-CONSTRUCTED POLYMERS AND RELATED METHODS - Patent application

Abstract

Pressure-sensitive adhesives are described that include polymers having the structure. Also described are various methods for making the described polymers and pressure-sensitive adhesives. Additionally, various articles, including tapes, that utilize the pressure-sensitive adhesives are described.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Application No. 63 / 384,347, filed November 18, 2022, which is incorporated herein by reference in its entirety.

[0002] The subject matter of this disclosure relates to methods for preparing polymers and pressure-sensitive adhesives having novel architectures characterized by long chain branching. The subject matter of this disclosure also relates to pressure-sensitive adhesives formed from the methods. Additionally, the subject matter of this disclosure relates to tapes and other articles employing the pressure-sensitive adhesives. [Background technology]

[0003] Solvent-based acrylic pressure-sensitive adhesives (PSAs) are used in high-performance applications because they offer a good balance of peel adhesion and cohesive strength. The polymers that make up these adhesives typically have high molecular weights, and the adhesives are characterized by high relative viscosities. Therefore, to make the polymers coatable at ambient temperatures, they must be diluted with a solvent. They are typically coated at 30-40% solids by weight. The solvent is removed (evaporated) immediately after the coating process.

[0004] The lower the solids content of a solvent-based adhesive, the longer it takes for the solvent to evaporate (or drive off) after coating. Therefore, to achieve a solvent-free coating without defects such as bubbles or skinning, very slow line speeds must be used during the coating process. As a result, the manufacturing costs of solvent-based acrylic products are high.

[0005] Acrylic hot melt or warm melt adhesives were developed to rival the adhesive performance of solvent-based adhesives while lowering coating costs by increasing line speeds. The molecular weight of these adhesives must be lower than traditional solvent-based acrylics to ensure the adhesive's viscosity (at 100% solids content) remains in a processable range. This low molecular weight leads to poor cohesion, as evidenced by poor shear performance. Therefore, the adhesive must be crosslinked after coating. Unfortunately, excessive crosslinking reduces the adhesive's peel and tack properties.

[0006] There is a continuing need for polymers that can be prepared for use in a variety of applications over a wide molecular weight range, such as, but not limited to, high molecular weight, high performance PSAs with an excellent balance of peel adhesion and cohesive strength, as well as compositions that can be rapidly coated and crosslinked to form such PSAs, particularly compositions that can be coated both as hot or warm melts and as high solids content coatings. Summary of the Invention

[0007] The difficulties and shortcomings associated with previous approaches are addressed by the subject matter of this disclosure as follows.

[0008] Described herein are polymer compositions having a structure, as well as methods for making and using the same. In some embodiments, the presently disclosed subject matter provides a polymer composition comprising, consisting essentially of, or consisting of a crosslinkable reaction product prepared by reacting or copolymerizing, or resulting from, a mixture comprising, consisting essentially of, or consisting of the following components: (1) one or more monomers comprising a single polymerizable ethylenically unsaturated bond, wherein the one or more monomers are selected from the group consisting of (meth)acrylates, (meth)acrylamides, non-(meth)acrylates, and combinations thereof; (2) one or more initiators; and (3) a functionalizing agent comprising one or more functional groups, wherein the crosslinkable reaction product comprises a polymer composition selected from the group consisting of a first polymer, a second polymer, and combinations thereof, and wherein the crosslinkable reaction product exhibits the following properties (A) through (D) when measured by gel permeation chromatography-multiangle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the polymer in tetrahydrofuran (THF) solution at 30° C.: (A) the polymer has a weight average absolute molecular weight (Mw) in the range of about 10,000 to about 10,000,000 g / mol; (B) the polymer has a polydispersity index (PDI) of about 4.0 or less; (C) The polymer is represented by the Mark-Houwink-Sakurada formula: [η]=KM α (where [η] is the intrinsic viscosity of a polymer of absolute molecular weight M) The alpha value calculated according to is less than approximately 0.70; (D) The polymer has the formula: g' w =[ηb] / [ηl] (where [ηb] is the intrinsic viscosity of the polymer, and [ηl] is the intrinsic viscosity of a reference linear polymer measured under the same solvent and temperature conditions, both having the same molecular weight (M), the molecular weight being measured by GPC-MALS-DV). The weight-average branching ratio g' is calculated according to w is approximately 0.90 or less; applies to the polymer.

[0009] In some embodiments, the polymer is as described above and has a weight average absolute molecular weight (Mw) of greater than about 300,000 g / mol when the polymer is in tetrahydrofuran (THF) solution at 30° C., as measured by GPC-MALS-DV.

[0010] In some embodiments, the polymer is as described above and has a weight average absolute molecular weight (Mw) in the range of about 400,000 to about 10,000,000 g / mol when the polymer is in tetrahydrofuran (THF) solution at 30° C., as measured by GPC-MALS-DV.

[0011] In some embodiments, the polymer is as described above, and the polymer has a polydispersity index (PDI) of from about 1.5 to about 4.0 or less when measured by GPC-MALS-DV when the polymer is in tetrahydrofuran (THF) solution at 30° C.

[0012] In some embodiments, the polymer is as described above and comprises, but is not limited to, a polymer in a state selected from the group consisting of star, dendritic, comb, brush, graft, pom-pom, hyperbranched polymers, and combinations thereof.

[0013] In some embodiments, the polymer forms an adhesive when at least partially crosslinked.

[0014] In some embodiments, the polymer is at least partially crosslinked, and has a plateau shear modulus of 10 or greater at 25° C. and 1 rad / sec, as measured by dynamic mechanical analysis (DMA). 4 ~10 7 dynes / cm 2 The adhesive is formed.

[0015] In some embodiments, the polymer, once polymerized, forms a pressure sensitive adhesive when at least partially crosslinked.

[0016] Also described herein are methods for producing such polymers with controlled architecture over a wide range of molecular weights.

[0017] The compositions and methods described herein overcome the limitations of current commercial products by creating polymers with controlled architecture that can be tailored for use in a variety of applications across a wide range of molecular weights, such as, but not limited to, high molecular weight, high performance PSAs with an excellent balance of peel adhesion and cohesive strength, and compositions that can be coated and crosslinked at high speeds to form such PSAs, particularly as hot melt or warm melt and high solids content coatings. DETAILED DESCRIPTION OF THE INVENTION

[0018] I. Definition The accompanying drawings are representative of some, but not all, embodiments described herein. The claims should not be construed as limited to the embodiments described herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. Like numbers refer to like elements throughout the specification.

[0019] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise.

[0020] As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably. Thus, for example, a composition comprising an additive can be interpreted to mean that the composition contains "one or more" additives.

[0021] The terms "preferred" and "preferably" refer to embodiments of the invention that may offer certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

[0022] Also herein, the recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5). Further, the disclosure of a range includes the disclosure of all subranges subsumed within that broader range (e.g., 1 to 5 discloses 1 to 4, 1.5 to 4.5, and 1 to 2).

[0023] Unless otherwise specified, the term "weight percent" or "wt%" refers to the concentration or composition of a component based on the total weight of the composition and is expressed as a percentage.

[0024] Unless otherwise specified, the term "parts by weight" refers to the concentration of an ingredient or composition based on the total weight of the composition.

[0025] As used herein, "comprise(s)," "include(s)," "having," "has," "contain(s)," and variations thereof are intended to be open-ended transitional phrases, terms, or words that do not exclude the possibility of additional acts or structures.

[0026] The term "component" refers to any part of a composition, polymer, or coating that contains a particular characteristic or structure. Examples of components include compounds, monomers, oligomers, polymers, and the organic groups contained therein.

[0027] As used herein, the term "aliphatic" is defined to include alkyl, alkenyl, alkynyl, halogenated alkyl, and cycloalkyl groups, as defined above. A "lower aliphatic" group is a branched or unbranched aliphatic group having 1 to 10 carbon atoms.

[0028] As used herein, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, including, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. As used herein, a "lower alkyl" group is a saturated branched or unbranched hydrocarbon group having 1 to 10 carbon atoms. In some embodiments, alkyl groups having 1 to 4 carbon atoms can be used. An alkyl group may be a "substituted alkyl" in which one or more hydrogen atoms are replaced with a substituent such as a halogen, cycloalkyl, alkoxy, amino, hydroxyl, allyl, or carboxyl.

[0029] As used herein, the term "aryl" refers to any carbon-based aromatic group, including, but not limited to, phenyl, naphthyl, and other suitable aryl compounds. As used herein, the term "aryl" also includes "heteroaryl groups," which are defined as aromatic groups having at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. An aryl group may be unsubstituted or substituted with one or more groups, including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy groups.

[0030] As used herein, the term "cycloalkyl" refers to a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. As used herein, the term "heterocycloalkyl group" refers to a cycloalkyl group as defined above in which at least one of the ring carbon atoms is replaced with a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.

[0031] As used herein, the term "oligomer" refers to a polyester oligomer having a weight average absolute molecular weight (Mw) in the range of about 300 to about 20,000 g / mol as measured by GPC-MALS-DV.

[0032] As used herein, the terms "water-based" or "aqueous-based" can include solvents that contain at least a portion of water, or solvents that contain mostly water. In some embodiments, the term "aqueous-based" can consist of only water, only water and a dispersant, only water and a catalyst, or only water, a dispersant, and a catalyst. In some embodiments, the term "aqueous-based" can comprise water, additives (e.g., catalyst, dispersant, etc.), and a co-solvent, such as an alcohol. According to some embodiments, the aqueous continuous phase does not contain a co-solvent.

[0033] The term "syrup composition" refers to a solution of solute polyester macromer in one or more solvent monomer mixtures, which composition has a viscosity of 500-10,000 cPs at room temperature. As used herein, the terms "room temperature" or "ambient temperature" are used interchangeably and refer to a temperature within the range of about 15° C. to about 25° C., more typically about 22° C. (72° F.).

[0034] The term "solvent-based," as used herein, refers to a composition in which one or more components are dissolved or dispersed in a non-aqueous carrier or solvent.

[0035] As used herein, the term "liquid at room temperature" refers to a polymer that undergoes some degree of cold flow at room temperature. Cold flow is the distortion, deformation, or dimensional change that occurs in a material under continuous load at temperatures within its range of use. Cold flow is not due to thermal softening.

[0036] As used herein, the term "(meth)acrylate copolymer" refers to a polymer formed from acrylate and / or methacrylate monomers, or any combination thereof, in a polymer composition, where the monomers are esters of acrylic or methacrylic acid containing a polymerizable ethylene bond. The term also includes other types of monomers with ethylene bonds that can be copolymerized with the acrylate and methacrylate monomers.

[0037] As used herein, the term "polymer" can refer to a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" encompasses terms such as "homopolymer," "copolymer," etc.

[0038] As used herein, the terms "derived from" or "prepared by reaction of" or "reaction product of" refer to the polymerization of said monomers to form the referenced product, i.e., upon polymerization, the monomers present in the polymer are chemically distinct from the unreacted monomers.

[0039] As used herein, the term "inhibitor" refers to a molecule that interacts with the radical end of a polymer chain to stop the growth of free radical polymerization by removing the energy for continuing reaction with monomer.

[0040] As used herein, the term "ethylenically unsaturated" when describing a monomer or group refers to a monomer or group that contains a terminal ethylene group (H2C=CH-).

[0041] As used herein, the term "curing" refers to polymerization and / or crosslinking.

[0042] As used herein, the term "architecture polymer" or "polymer architecture" in polymer science refers to polymers that have been intentionally designed to have properties that deviate from strictly linear polymer chains.

[0043] As used herein, the term "melt viscosity" of a polymer at a given temperature is a measure of the rate at which polymer molecules can move relative to one another under shear.

[0044] As used herein, the term "intrinsic viscosity [η]" is a measure of the contribution of a polymer solute to the viscosity of a solution at a particular temperature.

[0045] As used herein, the term "hydrodynamic radius, Rh" is the radius of an equivalent sphere representing the average volume swept by a particle (molecule) moving randomly in solution.

[0046] II. Crosslinkable Reaction Products

[0047] In general, the presently disclosed subject matter provides polymer compositions comprising, consisting essentially of, or consisting of a crosslinkable reaction product prepared by reaction or copolymerization from or derived from a mixture comprising, consisting essentially of, or consisting of the following components (1), (2), and (3): (1) one or more monomers comprising or consisting of a single polymerizable ethylenically unsaturated bond; (2) one or more initiators; and (3) a functional agent comprising one or more functional groups; wherein the one or more monomers are selected from the group consisting of (meth)acrylates, (meth)acrylamides, non-(meth)acrylates, and combinations thereof, and the crosslinkable reaction product comprises a polymer composition selected from the group consisting of a first polymer, a second polymer, and combinations thereof; and When the polymer is present in a tetrahydrofuran (THF) solution at 30°C, the following characteristics (A) to (D) are exhibited by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV): (A) the polymer has a weight average absolute molecular weight (Mw) in the range of about 10,000 to about 10,000,000 g / mol; (B) the polymer has a polydispersity index (PDI) of about 4.0 or less; (C) The polymer is represented by the Mark-Houwink-Sakurada formula: [η]=KM α (where [η] is the intrinsic viscosity of a polymer of absolute molecular weight M) The alpha value calculated according to is less than approximately 0.70; (D) The polymer has the formula: g' w =[ηb] / [ηl] (where [ηb] is the intrinsic viscosity of the polymer, and [ηl] is the intrinsic viscosity of a reference linear polymer measured under the same solvent and temperature conditions, both having the same molecular weight (M), the molecular weight being measured by GPC-MALS-DV). The weight-average branching ratio g' is calculated according to w is approximately 0.90 or less; applies to the polymer.

[0048] In some embodiments, the polymer is as described above, and the following aspects (A)-(I) of the polymer, the first polymer, and / or the second polymer: (A) the polymer comprises a non-linear polymer; (B) the first polymer comprises a polymer selected from the group consisting of a linear polymer, a non-linear polymer, and combinations thereof; (C) the first polymer comprises a linear polymer; (D) the first polymer comprises a non-linear polymer; (E) the first polymer comprises a linear polymer and a non-linear polymer; (F) the first polymer and the second polymer are non-linear polymers; (G) the first polymer is less nonlinear than the second polymer; (H) the second polymer comprises a non-linear polymer; and (I) Nonlinear polymers are discrete molecules; Any one or more of the following are contemplated in this disclosure:

[0049] In some embodiments, the polymer is as described above and exhibits the following aspects (A)-(F) of the first polymer and / or the second polymer when measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the first polymer and / or the second polymer in tetrahydrofuran (THF) solution at 30° C.: (A) The first polymer has the Mark-Houwink-Sakurada formula: [η]=KM α where [η] is the intrinsic viscosity of the first polymer of absolute molecular weight M. The α value calculated according to is greater than approximately 0.50; (B) The first polymer has the formula: g' w =[ηb] / [ηl], where [ηb] is the intrinsic viscosity of the first polymer, and [ηl] is the intrinsic viscosity of a reference linear polymer measured under the same solvent and temperature conditions, both having the same molecular weight (M), as measured by GPC-MALS-DV. The weight-average branching ratio g' is calculated according to w is approximately 0.90 or greater; (C) The second polymer is a polymer that conforms to the Mark-Houwink-Sakurada equation: [η] = KM α (where [η] is the intrinsic viscosity of a polymer of absolute molecular weight M) The alpha value calculated according to is less than approximately 0.70; (D) The second polymer has the formula: g' w = [ηb] / [ηl], where [ηb] is the intrinsic viscosity of the second polymer, and [ηl] is the intrinsic viscosity of a reference linear polymer measured under the same solvent and temperature conditions, both having the same molecular weight (M), as measured by GPC-MALS-DV. The weight-average branching ratio g' is calculated according to w is approximately 0.90 or less; (E) the α value of the first polymer is greater than the α value of the second polymer; and (F) The first polymer has a weight average branching ratio g' of the second polymer w Weight-average branching ratio g' is greater than w having; Any one or more of the following are contemplated in this disclosure:

[0050] In some embodiments, the polymer is as described above, and the first polymer and / or the second polymer exhibits the following properties (A)-(R) when measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the first polymer and / or the second polymer in tetrahydrofuran (THF) solution at 30° C.: (A) the first polymer has an α value of from about 0.60 to about 0.75, inclusive, and the second polymer has an α value of from about 0.20 to about 0.6, inclusive; (B) the first polymer has a weight average branching ratio g' of about 0.70 or more to about 1.00 or less; w and the second polymer has a weight average branching ratio g' of from about 0.20 or greater to about 0.70 or less. w have value; (C) the first polymer has an α value greater than about 0.70; (D) the first polymer has an α value greater than about 0.60; (E) the first polymer has an α value greater than about 0.50; (F) the first polymer has an α value of about 0.70 to about 0.75; (G) the first polymer has an α value of about 0.60 to about 0.70; (H) the first polymer has an α value of about 0.50 to about 0.60; (I) the first polymer has a weight average branching ratio g' of about 0.80 or greater; w having; (J) the second polymer has an α value of less than about 0.60; (K) the second polymer has an α value of less than about 0.50; (L) the second polymer has an α value of less than about 0.40; (M) the second polymer has an α value of less than about 0.30; (N) the second polymer has an α value of less than about 0.20; (O) the second polymer has an α value of about 0.60 to about 0.70; (P) the second polymer has an α value of about 0.50 to about 0.60; (Q) the second polymer has an α value of about 0.40 to about 0.30; and (R) The second polymer has an α value of about 0.30 to about 0.20 Any one or more of the following are contemplated in this disclosure:

[0051] In some embodiments, the polymer is as described above and includes the following polymer aspects (A)-(E): (A) the polymer comprises a greater weight percent of the first polymer than the second polymer, based on the total weight of the polymer; (B) the polymer comprises 50% or more by weight of a first polymer; (C) the polymer comprises 60% or more by weight of a first polymer; (D) the polymer comprises 70% or more by weight of a first polymer; and (E) the polymer comprises 80% or more by weight of a first polymer; Any one or more of the following are contemplated in this disclosure:

[0052] In some embodiments, the polymer is as described above and exhibits the following aspects (A)-(R) of the polymer when measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the polymer in tetrahydrofuran (THF) solution at 30° C.: (A) the polymer has a weight average absolute molecular weight (Mw) greater than about 100,000 g / mol; (B) the polymer has a weight average absolute molecular weight (Mw) in the range of about 100,000 to about 10,000,000 g / mol; (C) the polymer has a weight average absolute molecular weight (Mw) greater than about 150,000 g / mol; (D) the polymer has a weight average absolute molecular weight (Mw) in the range of about 150,000 to about 10,000,000 g / mol; (E) the polymer has a weight average absolute molecular weight (Mw) greater than about 200,000 g / mol; (F) the polymer has a weight average absolute molecular weight (Mw) in the range of about 200,000 to about 10,000,000 g / mol; (G) the polymer has a weight average absolute molecular weight (Mw) greater than about 250,000 g / mol; (H) the polymer has a weight average absolute molecular weight (Mw) in the range of about 250,000 to about 10,000,000 g / mol; (I) the polymer has a weight average absolute molecular weight (Mw) greater than about 300,000 g / mol; (J) the polymer has a weight average absolute molecular weight (Mw) in the range of about 350,000 to about 10,000,000 g / mol; (K) the polymer has a weight average absolute molecular weight (Mw) greater than about 400,000 g / mol; (L) the polymer has a weight average absolute molecular weight (Mw) in the range of about 400,000 to about 10,000,000 g / mol; (M) the polymer has a weight average absolute molecular weight (Mw) greater than about 450,000 g / mol; (N) the polymer has a weight average absolute molecular weight (Mw) in the range of about 450,000 to about 10,000,000 g / mol; (O) the polymer has a weight average absolute molecular weight (Mw) greater than about 500,000 g / mol; (P) the polymer has a weight average absolute molecular weight (Mw) in the range of about 500,000 to about 10,000,000 g / mol; (Q) the polymer has a weight average absolute molecular weight (Mw) greater than about 550,000 g / mol; and (R) polymer has a weight average absolute molecular weight (Mw) in the range of about 550,000 to about 10,000,000 g / mol; Any one or more of the following are contemplated in this disclosure:

[0053] The polymer has a weight average absolute molecular weight (Mw) in the range of about 10,000 to about 10,000,000 g / mol, this range including all intermittent values ​​and ranges therein.

[0054] In some embodiments, the polymer is as described above and exhibits the following aspects (A)-(I) of the polymer when measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the polymer in tetrahydrofuran (THF) solution at 30° C.: (A) the polymer has a polydispersity index (PDI) of about 1.1 to about 4.0 or less; (B) the polymer has a polydispersity index (PDI) of about 3.5 or less; (C) the polymer has a polydispersity index (PDI) of about 1.1 to about 3.5 or less; (D) the polymer has a polydispersity index (PDI) of about 3.0 or less; (E) the polymer has a polydispersity index (PDI) of about 1.1 to about 3.0 or less; (F) the polymer has a polydispersity index (PDI) of about 2.5 or less; (G) the polymer has a polydispersity index (PDI) of about 1.1 to about 2.5 or less; (H) the polymer has a polydispersity index (PDI) of about 2.0 or less; and (I) the polymer has a polydispersity index (PDI) of about 1.1 to about 2.0 or less; Any one or more of the following are contemplated in this disclosure:

[0055] In some embodiments, the polymer is as described above and exhibits the following aspects (A)-(M) of the first polymer when measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the first polymer in tetrahydrofuran (THF) solution at 30° C.: (A) the first polymer has a weight average absolute molecular weight (Mw) that is less than the weight average absolute molecular weight (Mw) of the second polymer; (B) the first polymer has a weight average absolute molecular weight (Mw) of about 100,000 g / mol or greater; (C) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 100,000 to about 5,000,000 g / mol; (D) the first polymer has a weight average absolute molecular weight (Mw) of about 200,000 g / mol or greater; (E) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 200,000 to about 5,000,000 g / mol; (F) the first polymer has a weight average absolute molecular weight (Mw) of about 400,000 g / mol or greater; (G) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 400,000 to about 5,000,000 g / mol; (H) the first polymer has a weight average absolute molecular weight (Mw) of about 500,000 g / mol or greater; (I) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 500,000 to about 5,000,000 g / mol; (J) the first polymer has a weight average absolute molecular weight (Mw) of about 700,000 g / mol or greater; (K) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 700,000 to about 5,000,000 g / mol; (L) the first polymer has a weight average absolute molecular weight (Mw) of about 1,000,000 g / mol or greater; and (M) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 1,000,000 to about 5,000,000 g / mol; Any one or more of the following are contemplated in this disclosure:

[0056] The first polymer has a weight average absolute molecular weight (Mw) in the range of about 100,000 to about 5,000,000 g / mol, this range including all intermittent values ​​and ranges therein.

[0057] In some embodiments, the polymer is as described above and exhibits the following aspects (A)-(S) of the second polymer when measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the second polymer in tetrahydrofuran (THF) solution at 30° C.: (A) the second polymer has a weight average absolute molecular weight (Mw) greater than the weight average absolute molecular weight (Mw) of the polymer; (B) the second polymer has a weight average absolute molecular weight (Mw) greater than about 300,000 g / mol; (C) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 300,000 to about 30,000,000 g / mol; (D) the second polymer has a weight average absolute molecular weight (Mw) greater than about 600,000 g / mol; (E) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 600,000 to about 30,000,000 g / mol; (F) the second polymer has a weight average absolute molecular weight (Mw) greater than about 900,000 g / mol; (G) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 900,000 to about 30,000,000 g / mol; (H) the second polymer has a weight average absolute molecular weight (Mw) greater than about 1,200,000 g / mol; (I) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 1,200,000 to about 30,000,000 g / mol; (J) the second polymer has a weight average absolute molecular weight (Mw) greater than about 1,500,000 g / mol; (K) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 1,500,000 to about 30,000,000 g / mol; (L) the second polymer has a weight average absolute molecular weight (Mw) greater than about 3,000,000 g / mol; (M) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 3,000,000 to about 30,000,000 g / mol; (N) the second polymer has a weight average absolute molecular weight (Mw) greater than about 5,000,000 g / mol; (O) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 5,000,000 to about 30,000,000 g / mol; (P) the second polymer has a weight average absolute molecular weight (Mw) greater than about 6,000,000 g / mol; (Q) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 6,000,000 to about 30,000,000 g / mol; (R) the second polymer has a weight average absolute molecular weight (Mw) greater than about 9,000,000 g / mol; and (S) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 9,000,000 to about 30,000,000 g / mol; Any one or more of the following are contemplated in this disclosure:

[0058] The second polymer has a weight average absolute molecular weight (Mw) in the range of about 300,000 to about 30,000,000 g / mol, this range including all intermittent values ​​and ranges therein.

[0059] In some embodiments, the polymer is as described above and exhibits the following aspects (A)-(I) of the first polymer and / or the second polymer when measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the first polymer and / or the second polymer in tetrahydrofuran (THF) solution at 30° C.: (A) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 4.0 or less; (B) the first and / or second polymer has a polydispersity index (PDI) of about 3.5 or less; (C) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 3.5 or less; (D) the first and / or second polymer has a polydispersity index (PDI) of about 3.0 or less; (E) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 3.0 or less; (F) the first and / or second polymer has a polydispersity index (PDI) of about 2.5 or less; (G) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 2.5 or less; (H) the polydispersity index (PDI) of the first and / or second polymer is about 2.0 or less; and (I) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 2.0 or less; Any one or more of the following are contemplated in this disclosure:

[0060] In some embodiments, the polymer is as described above and exhibits the following aspects (A) through (W) of the polymer after polymerization when measured in a parallel plate rheometer at a temperature of about 140° C.: (A) Polymer is approximately 1.0 s -1having a first melt viscosity after polymerization of about 30,000 cps (30 Pa·s) or more at a shear rate of (B) The polymer is approximately 1.0 s -1 having a first melt viscosity after polymerization of about 40,000 cps (40 Pa·s) or greater at a shear rate of (C) The polymer is approximately 1.0 s -1 having a first melt viscosity after polymerization of about 50,000 cps (50 Pa·s) or more at a shear rate of (D) The polymer is approximately 1.0 s -1 having a first melt viscosity after polymerization of about 60,000 cps (60 Pa·s) or greater at a shear rate of (E) The polymer is approximately 1.0 s -1 having a first melt viscosity after polymerization of about 70,000 cps (70 Pa·s) or more at a shear rate of (F) Polymer is approximately 1.0 s -1 having a first melt viscosity after polymerization of about 80,000 cps (80 Pa·s) or greater at a shear rate of (G) Polymer is approximately 1.0 s -1 having a first melt viscosity after polymerization of about 90,000 cps (90 Pa·s) or greater at a shear rate of (H) Polymer is approximately 1.0 s -1 having a first melt viscosity after polymerization of about 100,000 cps (100 Pa·s) or greater at a shear rate of (I) The polymer is approximately 1.0 s -1 having a first melt viscosity after polymerization of about 200,000 cps (200 Pa·s) or greater at a shear rate of (J) Polymer is approximately 1000s -1 at a shear rate of about 1,000 cps (1 Pa·s) or more after polymerization; (K) Polymer is approximately 1000s -1 at a shear rate of about 2,000 cps (2 Pa·s) or more after polymerization; (L) Polymer is approximately 1000s -1having a second melt viscosity after polymerization of about 5,000 cps (5 Pa·s) or more at a shear rate of (M) Polymer is approximately 1000s -1 having a second melt viscosity after polymerization of about 10,000 cps (10 Pa·s) or more at a shear rate of (N) Polymer is approximately 1000s -1 having a second melt viscosity after polymerization of about 15,000 cps (15 Pa·s) or more at a shear rate of (O) Polymer is approximately 1000s -1 having a second melt viscosity after polymerization of about 20,000 cps (20 Pa·s) or more at a shear rate of (P) Polymer is approximately 1000s -1 having a second melt viscosity after polymerization of about 30,000 cps (30 Pa·s) or more at a shear rate of (Q) The polymer is approximately 1000s -1 having a second melt viscosity after polymerization of about 40,000 cps (40 Pa·s) or more at a shear rate of (R) polymer is approximately 1000s -1 having a second melt viscosity after polymerization of about 50,000 cps (50 Pa·s) or more at a shear rate of (S) polymer is approximately 1.0s -1 and a first melt viscosity after polymerization in the range of about 30,000 cps (30 Pa·s) to about 4,000,000 cps (4,000 Pa·s) at a shear rate of about 1,000 s -1 a second melt viscosity in the range of about 1,000 cps (1 Pa·s) to about 200,000 cps (200 Pa·s) at a shear rate of; (T) polymer is approximately 1.0s -1 and a first melt viscosity after polymerization in the range of about 30,000 cps (30 Pa·s) to about 4,000,000 cps (4,000 Pa·s) at a shear rate of about 1,000 s -1 a second melt viscosity in the range of about 15,000 cps (15 Pa·s) to about 200,000 cps (200 Pa·s) at a shear rate of (U) Polymer is approximately 1.0s -1 and a first melt viscosity after polymerization in the range of about 30,000 cps (30 Pa·s) to about 4,000,000 cps (4,000 Pa·s) at a shear rate of about 1,000 s -1 a second melt viscosity in the range of about 40,000 cps (40 Pa·s) to about 200,000 cps (200 Pa·s) at a shear rate of (V) Polymer is about 1.0s -1 and a first melt viscosity after polymerization in the range of about 100,000 cps (100 Pa·s) to about 4,000,000 cps (4,000 Pa·s) at a shear rate of about 1000 s -1 a second melt viscosity in the range of about 15,000 cps (15 Pa s) to about 200,000 cps (200 Pa s) at a shear rate of (W) polymer is approximately 1.0s -1 and a first melt viscosity after polymerization in the range of about 100,000 cps (100 Pa·s) to about 4,000,000 cps (4,000 Pa·s) at a shear rate of about 1000 s -1 a second melt viscosity in the range of about 40,000 cps (40 Pa·s) to about 200,000 cps (200 Pa·s) at a shear rate of Any one or more of the following are contemplated in this disclosure:

[0061] In some embodiments, the polymer is as described above and can be prepared by the free radical polymerization reaction of a mixture comprising or consisting of: (1) about 80 to about 99 weight percent of one or more monomers comprising or consisting of a single polymerizable ethylenically unsaturated bond; (2) about 0.001 to about 5 weight percent of one or more initiators; and (3) about 0.001 to about 5 weight percent of a functional group agent; where the weight percents of the components add up to 100% based on the total weight of the polymer.

[0062] A. Monofunctional Monomers

[0063] In some embodiments, the polymer is as described above, and the mixture polymerized to form the polymer described herein comprises or consists of from about 80 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 82 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 84 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 85 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 86 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 88 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 89 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 90 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 91 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 92 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 93 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 94 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 95 to about 99 wt. % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively from about 96 to about 99 wt. % (in The composition may comprise or consist of from about 86 to about 99% by weight (including all intermittent values ​​and ranges therein), from about 88 to about 99% by weight (including all intermittent values ​​and ranges therein), or alternatively from about 90 to about 99% by weight (including all intermittent values ​​and ranges therein), or alternatively from about 92 to about 99% by weight (including all intermittent values ​​and ranges therein), or alternatively from about 94 to about 99% by weight (including all intermittent values ​​and ranges therein), or alternatively from about 96 to about 99% by weight (including all intermittent values ​​and ranges therein).

[0064] In some embodiments, the polymer is as described above, wherein the one or more monomers are selected from the group consisting of acrylic acid, acrylates comprising a C1 to about C20 alkyl, aryl, aralkyl, or cyclic acrylate, acrylamides comprising a C1 to about C20 alkyl, aryl, aralkyl, or cyclic acrylamide, methacrylic acid, methacrylates comprising a C1 to about C20 alkyl, aryl, aralkyl, or cyclic methacrylate, methacrylamides comprising a C1 to about C20 alkyl, aryl, aralkyl, or cyclic methacrylamide, vinyl monomers, olefins, vinyl aromatics, (meth)acrylated urethanes, (meth)acrylated carbonates, (meth)acrylated esters, (meth)acrylated esters, vinyl esters, vinyl pyrrolidone, styrene, and combinations thereof.

[0065] In some embodiments, the polymer is as described above and comprises one or more of the following monomer aspects (A) through (G): (A) the conversion of one or more monomers is at least about 90%; (B) the one or more monomers further comprise one or more crosslinkable functional groups, the crosslinkable functional groups being selected from the group consisting of actinically active functional groups, self-reactive functional groups, reactive functional groups, and combinations thereof; (C) the actinically active functional group is activatable using actinic or electron beam radiation; (D) the actinically active functional group is selected from the group consisting of benzophenone, double bond, and combinations thereof; (E) the actinically active functional group is selected from the group consisting of acetophenone, acetophenone derivatives, benzophenone, benzophenone derivatives, anthraquinone, anthraquinone derivatives, benzil, benzil derivatives, thioxanthone, thioxanthone derivatives, xanthone, xanthone derivatives, benzoin ethers, benzoin ether derivatives, α-ketol, α-ketol derivatives, and combinations thereof; (F) the reactive functional group is selected from the group consisting of hydroxyl, carboxyl, carbonyl, carbonate ester, isocyanate, epoxy, vinyl, amine, amide, imide, anhydride, mercapto (thiol), acid, acrylamide, acetoacetyl group, alkoxymethylol, cyclic ether group, and combinations thereof; and (G) the self-reactive functional group is selected from the group consisting of silane, silyl, anhydride, epoxy, alkoxymethylol, and cyclic ether; Any one or more of the following are contemplated in this disclosure:

[0066] B. Initiator

[0067] In some embodiments, the polymer is as described above, and the mixture polymerized to form the polymer described herein comprises from about 0.001 to about 5 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 0.1 to about 5 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 0.5 to about 5 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 1.0 to about 5 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 1.5 to about 5 wt % (including all intermittent values ​​and ranges therebetween). %, or alternatively, about 2.0 to about 5% by weight (including all intermittent values ​​and ranges therein), or alternatively about 2.5 to about 5% by weight, or alternatively about 3.0 to about 5% by weight (including all intermittent values ​​and ranges therein), or alternatively about 3.5 to about 5% by weight (including all intermittent values ​​and ranges therein), or alternatively about 4.0 to about 5% by weight (including all intermittent values ​​and ranges therein), or alternatively about 4.5 to about 5% by weight (including all intermittent values ​​and ranges therein).

[0068] In some embodiments, the polymer is as described above and is selected from the group consisting of actinically activated initiators, electron beam radiation activated initiators, thermally activated initiators, redox initiators, electrochemical initiators, and combinations thereof.

[0069] In some embodiments, the polymer is as described above and includes the following aspects (A) to (N) of the polymerization initiator and / or crosslinking initiator: (A) Both the polymerization initiator and the crosslinking initiator are actinically activated initiators; (B) the polymerization initiator is activatable at a first activation wavelength; (C) the cross-linking initiator is activatable at a second activation wavelength; (D) the polymerization initiator is selectively activatable in the presence of the cross-linking initiator without activating the cross-linking initiator; (E) the polymerization initiator is selectively activatable in the presence of the crosslinking initiator without activating the crosslinking initiator and without the use of an optical filter; (F) the polymerization initiator is selectively activatable in the presence of the cross-linking initiator without activating the cross-linking initiator and using an optical filter; (G) the optical filter is selected from the group consisting of an absorptive filter, a dichroic filter (or two-color filter), a polychroic filter (or multicolor filter), a notch filter, a short-pass filter, a long-pass filter, a band-pass filter, a multiple-band filter (e.g., a triple-band filter), and combinations thereof; (H) the optical filter is selected from a polymer layer, a lens, a film, and combinations thereof; (I) the polymerization initiator is substantially non-photoactive at the activation wavelength of the crosslinking initiator; (J) the crosslinking initiator is substantially non-photoactive at the activation wavelength of the polymerization initiator; (K) at least one of the polymerization initiator and the crosslinking initiator comprises a polymerizable monomer containing a photoinitiator moiety; (L) the polymerization initiator is a thermally activated initiator and the crosslinking initiator is an actinically activated initiator; (M) the polymerization initiator is an actinically activated initiator, and the crosslinking initiator is at least one of a thermally activated initiator and an actinically activated initiator; and (N) the polymerization initiator is at least one of a thermally activated initiator and an actinically activated initiator, and the crosslinking initiator is at least one of a thermally activated initiator and an actinically activated initiator; Any one or more of the following are contemplated in this disclosure:

[0070] C. Functional group agents

[0071] In some embodiments, the polymer is as described above, and the mixture polymerized to form the polymer described herein comprises from about 0.001 to about 5 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 0.1 to about 5 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 0.5 to about 5 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 1.0 to about 5 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 1.5 to about 5 wt % (including all intermittent values ​​and ranges therebetween), or alternatively Alternatively, the composition may comprise or consist of about 2.0 to about 5 wt. % (including all intermittent values ​​and ranges therein), or alternatively, about 2.5 to about 5 wt. % (including all intermittent values ​​and ranges therein), or alternatively, about 3.0 to about 5 wt. % (including all intermittent values ​​and ranges therein), or alternatively, about 3.5 to about 5 wt. % (including all intermittent values ​​and ranges therein), or alternatively, about 4.0 to about 5 wt. % (including all intermittent values ​​and ranges therein), or alternatively, about 4.5 to about 5 wt. % (including all intermittent values ​​and ranges therein) of a functional group agent.

[0072] In some embodiments, the polymer is as described above and includes the following aspects (A) through (J) of the functional group agent: (A) The functional group agent is (a) a multifunctional initiator, (b) multifunctional chain transfer agents (CTAs); (c) polyfunctional monomers, (d) a linear polymer or oligomer comprising one or more multifunctional initiators chemically attached onto the polymer or oligomer backbone; and (e) Linear polymers or linear oligomers comprising / having / including two or more monofunctional initiators chemically attached onto the polymer or oligomer backbone, and combinations thereof. selected from the group consisting of: (B) the functional group agent comprises a multifunctional chain transfer agent; (C) the functional agent comprises three or more functional groups; (D) other than the functionalizing agent, the mixture does not contain any other monomers comprising two or more polymerizable ethylenically unsaturated bonds (i.e., the formation of certain embodiments of controlled non-linear architectures is achieved solely through the functionalizing agent, in contrast to the prior art where random non-linear architectures are achieved, for example, through both the multifunctional CTA and the multifunctional monomer); (E) Multifunctional chain transfer agents comprise two or more functional groups, the functional groups having the same or different reactivities; (F) The polyfunctional chain transfer agent comprises a polyvalent mercaptan core comprising three or more thiol (SH) groups, the thiol groups having the same or different reactivities; (G) Functional agents comprise polyvalent or polyfunctional atoms or molecules (e.g., halogens, CCl4, etc.); (H) the functional group agent comprises a polyhydric or polyfunctional mercaptan; (I) the functional group agent comprises a derivative of a thiocarboxylic acid; and (J) the functional group agent is derived from a polythiocarboxylic acid selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), dipentaerythritol hexakis(3-mercaptopropionate) (DPMP), trimethylolpropane tris(3-mercaptopropionate) (TMMP), and tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate (TEMPIC), and combinations thereof; Any one or more of the following are contemplated in this disclosure:

[0073] Without being bound by any theory, it is believed that one or more monomers are polymerizable with the functional groups of the functionalizing agent to form (i) a linear polymer, (2) a functionalized linear polymer (e.g., comb, brush, graft polymer), and / or (3) a non-linear polymer. A functionalized linear polymer comprises pendant side-chain polymeric arms attached to a linear polymer backbone (e.g., brush, comb, graft polymer, etc.).

[0074] D. Coupling Agent

[0075] The above-described mixtures polymerized to form the polymers described herein may contain less than about 0.5 wt % (inclusive of all intermittent values ​​and ranges therebetween), alternatively from about 0.001 to about 0.5 wt % (inclusive of all intermittent values ​​and ranges therebetween), alternatively from about 0.001 to about 0.4 wt % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively less than 0.3 wt %, or alternatively from about 0.001 to about 0.29 wt % (inclusive of all intermittent values ​​and ranges therebetween), ...4 wt % (inclusive of all intermittent values ​​and ranges therebetween), or alternatively less than 0.3 wt % The composition may comprise or consist of from about 0.01 to about 0.29 wt. % coupling agent (including all intermittent values ​​and ranges therein), 0.1 to about 0.29 wt. % coupling agent (including all intermittent values ​​and ranges therein), or alternatively from about 0.15 to about 0.29 wt. % coupling agent (including all intermittent values ​​and ranges therein), or alternatively from about 0.20 to about 0.29 wt. % coupling agent (including all intermittent values ​​and ranges therein), or alternatively from about 0.25 to about 0.29 wt. % coupling agent (including all intermittent values ​​and ranges therein).

[0076] In some embodiments, the polymer is as described above and the following aspects (A) through (J) of the coupling agent are present: (A) the coupling agent comprises a monomer; (B) the coupling agent comprises at least one polymerizable ethylenically unsaturated bond; (C) the coupling agent comprises two or more polymerizable ethylenically unsaturated bonds (e.g., a divinyl monomer); (D) The coupling agent cannot participate in a free radical polymerization reaction; (E) the coupling agent comprises a functional group capable of reacting under non-free radical conditions in a condensation reaction; (F) the coupling agent is capable of participating in a free radical process; (G) the coupling agent comprises a cationically polymerizable group; (H) the coupling agent comprises a vinyl ether group; (I) The coupling agent is capable of undergoing a thiol-ene reaction; (J) Coupling agents include aliphatic divinyl compounds such as divinyl ether, diisocyanate, polyfunctional (meth)acrylate, bifunctional (meth)acrylate, hexa-1,5-diene, hepta-1,6-diene, ethylene glycol dimethacrylate, methylene di(meth)acrylate, and ethylenedivinylurea; aromatic divinyl compounds such as divinylbenzene, methyldivinylbenzene, divinyltoluene, divinylbiphenyl, diallyl phthalate, and divinylnaphthalene; polyhydric ethylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate; polyhydric propylene glycol di(meth)acrylates such as propylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate; dimethacrylate compounds such as ricol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-methyl-1,8-octanediol (meth)acrylate, and 1,4-cyclohexanediol dimethacrylate; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate and ethylene glycol dimethacrylate; divinyl compounds such as divinyl ether, divinyl sulfite, divinyl sulfone, and N,N'-methylenebisacrylamide, and combinations thereof; Any one or more of the following are contemplated in this disclosure:

[0077] Without being bound by any theory, it is believed that the coupling agent can covalently bond each of the cores of some of the polymers to one or more other cores to form at least one of a pom-pom-like chain polymer structure and / or a multidimensional network structure, resulting in a significant increase in the molecular weight of the resulting polymer.

[0078] E. Multifunctional Agents

[0079] The above-described mixtures polymerized to form the polymers described herein contain less than 0.5 wt. %, or alternatively, from about 0.001 to about 0.5 wt. %, (including all intermittent values ​​and ranges therebetween), or alternatively, from about 0.001 to about 0.4 wt. %, (including all intermittent values ​​and ranges therebetween), or alternatively, less than 0.3 wt. %, (including all intermittent values ​​and ranges therebetween), or alternatively, from about 0.001 to about 0.29 wt. %, (including all intermittent values ​​and ranges therebetween), or alternatively, from about 0.001 to about 0.29 wt. %, (including all intermittent values ​​and ranges therebetween), or alternatively, from about 0.001 to about 0.4 wt. %, (including all intermittent values ​​and ranges therebetween), or alternatively, from about 0.001 to about 0.4 wt. %, (including all intermittent values ​​and ranges therebetween), or alternatively, from about 0.001 to about 0.29 ...4 wt. %, (including all intermittent values ​​and ranges therebetween), or alternatively, from about 0.001 to about 0.29 w The composition may further comprise or consist of from about 0.01 to about 0.29 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 0.1 to about 0.29 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 0.15 to about 0.29 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 0.20 to about 0.29 wt % (including all intermittent values ​​and ranges therebetween), or alternatively from about 0.25 to about 0.29 wt % (including all intermittent values ​​and ranges therebetween) of a polyfunctional agent.

[0080] In some embodiments, the polymer is as described above and includes the following aspects (A) through (K) of the multifunctional agent: (A) the one or more multifunctional agents are monomers; (B) The polyfunctional agent chemically bonds to the polymer backbone; (C) the polyfunctional agent comprises at least one ethylenically unsaturated bond; (D) the polyfunctional agent comprises two or more ethylenically unsaturated bonds; (E) the multifunctional agent comprises at least one of ethylenic unsaturation and acrylate unsaturation; (F) the polyfunctional agent comprises a functional group capable of reacting under non-free radical conditions in a condensation reaction; (G) The multifunctional agent is capable of undergoing a thiol-ene reaction; (H) The polyfunctional agent comprises at least one radically polymerizable group and at least one cationically polymerizable group in one molecule; (I) The polyfunctional agent comprises at least one (meth)acryloyl group and at least one vinyl ether group in one molecule; (J) The polyfunctional agent can be represented by the following formula (I): TIFF2025538463000001.tif2063[where, R 1 is hydrogen; aliphatic C 1~6 Alkyl; and C 1~6 cycloalkyl; R 2 is C 2~20 Alkylene; C 2~20 a hydrocarbon diradical; and a polyalkylene oxide; and R 3 is selected from hydrogen and methyl; and (K) the multifunctional agent is selected from the group consisting of multifunctional (meth)acrylates, allyl (meth)acrylates, vinyl ether (meth)acrylates, α-olefin maleic anhydrides (AOMA), 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA), 2-(2′-vinyloxyethoxy)ethyl methacrylate (VEEM), 2-vinyloxyethyl acrylate, 2-vinyloxyethyl methacrylate, 2-(2′-prop-1-enyloxyethoxy)ethyl methacrylate, 2-(2′-prop-1-enyloxyethoxy)ethyl acrylate, and combinations thereof; Any one or more of the following are contemplated in this disclosure:

[0081] Without being bound by any theory, it is believed that the molecular weight of the above-described polymers can be significantly increased by the following reaction:

[0082] (1) one or more multifunctional agents are polymerizable (e.g., via a free radical polymerization reaction) with one or more monomers (through (meth)acrylate groups) to form one or more pendant side chains attached to a functionalized linear polymer backbone, the one or more pendant side chains each comprising a vinyl group. The vinyl groups of the one or more pendant side chains can react with at least one of the functional groups of the functional agent to form one or more non-linear polymers, the one or more non-linear polymers comprising one or more pendant side chains covalently attached to the functionalized linear polymer backbone; and

[0083] (2) One or more multifunctional agents are polymerizable (through the vinyl group) with at least one of the functional groups of the functional agent (e.g., via a thiol-ene reaction) to form one or more multifunctional chain transfer agents, each of which comprises a (meth)acrylate group. The one or more multifunctional chain transfer agents are polymerizable (through the (meth)acrylate group) with one or more monomers to form one or more pendant side chains, which are covalently attached to the functionalized linear polymer backbone to form a non-linear polymer.

[0084] The resulting non-linear polymer may comprise at least one of a comb polymer / structure, a brush polymer / structure, and a graft polymer / structure.

[0085] In some embodiments, the polymer is as described above, and the composition may further comprise or consist of a ring-opening monomer selected from the group consisting of epoxies, oxetanes, anhydrides, lactones, lactams, cyclic ethers, and cyclic siloxanes, and combinations thereof, and a cationically polymerizable monomer selected from the group consisting of epoxy-containing materials, alkyl vinyl ethers, cyclic ethers, styrene, divinylbenzene, vinyl toluene, N-vinyl compounds, cyanate esters, 1-alkyl olefins (α-olefins), lactams, and cyclic acetals, and combinations thereof.

[0086] In some embodiments, the polymer is as described above and the composition may further comprise or consist of at least one component selected from the group consisting of pigments, tackifiers, plasticizers, fillers, diluents, suppressors, and combinations thereof.

[0087] In some embodiments, the polymer is as described above, and the following aspects (A)-(F) of the mixture are polymerized to form the polymer described herein: (A) the mixture further comprises a non-reactive carrier; (B) the mixture does not contain a nonreactive carrier; (C) A nonreactive carrier does not react with the functional groups of the components of the mixture; (D) the non-reactive carrier is selected from the group consisting of organic solvents, water, and combinations thereof; (E) the organic solvent is selected from the group consisting of aromatic hydrocarbons, alkyl esters, cycloaliphatic hydrocarbons, aliphatic hydrocarbons, ketones, amines, amides, esters, ethers, aliphatic esters, alcohols, nitrated hydrocarbons, unsaturated hydrocarbons, chlorinated hydrocarbons, and combinations thereof; and (F) the mixture has a pre-polymerization viscosity of about 2 cps to about 50 cps at room temperature; Any one or more of the following are contemplated in this disclosure:

[0088] In some embodiments, the polymer is as described above and is prepared by the following aspects (A) through (G) of the above free radical polymerization reaction: (A) The reaction is a solvent polymerization reaction; (B) The reaction is a non-solution process; (C) The reaction is an emulsion polymerization reaction; (D) The reaction is a bulk polymerization reaction; (E) The reaction is a suspension polymerization reaction; (F) the reaction is a one-step process; and (G) The reaction is a two-step or more-step process; Any one or more of the following are contemplated in this disclosure: For example, a linear polymer or oligomer comprising one or more multifunctional initiators chemically attached onto the polymer or oligomer backbone, or a linear polymer or oligomer comprising two or more monofunctional initiators chemically attached onto the polymer or oligomer backbone, can be subjected to further polymerization or modification steps to form a non-linear polymer.

[0089] In some embodiments, the polymer is as described above, and the polymer has the following aspects (A)-(J): (A) The polymer is soluble in a non-reactive carrier; (B) Conversion of monomer to polymer is greater than 90%; (C) the polymer has a multimodal molecular weight distribution as measured by GPC-MALS-DV; (D) The polymer is 100% solids; (E) The polymer is not gelled (gel-free); (F) the polymer has a unimodal molecular weight distribution as measured by GPC-MALS-DV; (G) the polymer has a multimodal molecular weight distribution as measured by GPC-MALS-DV; (H) the polymer has a glass transition temperature (Tg) of about 100°C to about -115°C as measured by differential scanning calorimetry (DSC); (I) the polymer has a single glass transition temperature (Tg) within the range of about 100°C to about -115°C, as measured by differential scanning calorimetry (DSC); and (J) the polymer has two or more glass transition temperatures (Tg) within the range of about 100°C to about -115°C as measured by differential scanning calorimetry (DSC); Any one or more of the following are contemplated in this disclosure:

[0090] III. Crosslinked Reaction Products

[0091] In some embodiments, the polymers described above may be at least partially crosslinked via at least one of actinic radiation, electron beam radiation, heat, moisture (or humidity), or metal-based ionic crosslinking to form an adhesive.

[0092] In some embodiments, the polymer is as described above, and upon at least partial crosslinking, the polymer exhibits any one or more of the following aspects (A)-(C), also contemplated herein: (A) the polymer is at least partially crosslinked to form an adhesive; (B) The polymer is at least partially crosslinked and has a plateau shear modulus of 10 at 25° C. and 1 rad / sec as measured by dynamic mechanical analysis (DMA). 4 ~10 7 dynes / cm 2 forming an adhesive which is (C) The polymer is at least partially crosslinked to form a pressure sensitive adhesive.

[0093] In some embodiments, the polymer is as described above and the at least partial crosslinking of the polymer is effected by heating the composition.

[0094] In some embodiments, the polymer is as described above and at least partially crosslinked via metal-based ionic crosslinks.

[0095] In some embodiments, the polymer is as described above and the at least partial crosslinking is effected by exposing the composition to actinic or electron beam radiation.

[0096] Pressure sensitive adhesives comprising the above polymers are also contemplated by the present disclosure.

[0097] According to what has become known as the Dahlquist criterion, to function as a pressure-sensitive adhesive, a formulation must have a plateau shear modulus of 5 x 10 at 1 rad / sec at 25 °C, as measured by dynamic mechanical analysis. 4 ~6×10 6 dynes / cm 2 The plateau shear modulus at 25°C must be 1 x 10 7 dynes / cm 2 Larger materials are too stiff to exhibit the tack required for use as pressure-sensitive adhesives at room temperature. Plateau shear modulus at 25°C is 1 x 10 4 dynes / cm 2 Materials below this temperature lack sufficient cohesive strength to be useful as pressure-sensitive adhesives. Representative, non-limiting examples of ranges of glass transition temperatures (Tg) measured by DSC for pressure-sensitive adhesives of the present disclosure include from about 10°C to about -60°C, or from about 0°C to about -40°C, and / or from about -10°C to about -40°C.

[0098] Polymer blends comprising first and second polymers as described above and as defined in any one of claims 1 to 26 are also contemplated by the present disclosure.

[0099] Articles comprising the above adhesives are also contemplated by the present disclosure.

[0100] In some embodiments, the article further comprises a substrate defining a surface; The adhesive can be applied (or spread) directly onto at least a portion of the surface of the substrate and does not require a primer to be placed between the adhesive and the substrate. In some embodiments, the substrate is heat sensitive (i.e., degrades, melts, bends, bubbles) at temperatures above about 110°C, and the substrate is selected from the group consisting of polypropylene, polyethylene, and vinyl, wherein the polyethylene is selected from the group consisting of linear density polyethylene (LDPE), linear low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), and combinations thereof.

[0101] In some embodiments, the article further comprises a substrate defining a surface; The adhesive can be coated onto a carrier or release liner which is then transferred to the substrate, the carrier being selected from the group consisting of silicone coated paper, polyethylene film, polyester film, glassine paper, polycoated kraft paper, fluoropolymer film, release coated fabrics, thermoplastic film, polypropylene film, release coated foil, and polyvinyl chloride (PVC) film.

[0102] In some embodiments, a method of forming a composition comprising a crosslinkable polymer as described above is contemplated, comprising the steps of: (1) providing a mixture of components according to any one of claims 1-26; and (2) polymerizing the mixture via a free radical polymerization reaction to form a polymer according to any one of claims 1-26.

[0103] In some embodiments, the polymerizing step comprises heating the mixture.

[0104] In some embodiments, the polymerizing step comprises exposing the mixture to actinic or electron beam radiation.

[0105] In some embodiments, the polymerization process is carried out in one step.

[0106] In some embodiments, the polymerization process is carried out in two or more stages.

[0107] The method further comprises (3) crosslinking the polymer to form the adhesive, the crosslinking being activatable by at least one of actinic radiation, electron beam radiation, heat, moisture (or humidity), or metal-based ionic crosslinking.

[0108] In some embodiments, the adhesive has a viscosity of 10 at 1 rad / sec at 25° C. as measured by dynamic mechanical analysis (DMA). 4 ~10 7 dynes / cm 2 has a plateau shear modulus of

[0109] In some embodiments, the adhesive is a pressure sensitive adhesive. In some embodiments, the presently disclosed subject matter provides polymer compositions comprising, consisting essentially of, or consisting of a crosslinkable reaction product prepared by reacting, copolymerizing, or resulting from a mixture comprising, consisting essentially of, or consisting of the following components (1) through (3): (1) one or more monomers comprising or consisting of a single polymerizable ethylenically unsaturated bond, wherein the one or more monomers are selected from the group consisting of (meth)acrylates, (meth)acrylamides, non-(meth)acrylates, and combinations thereof; (2) one or more initiators; and (3) a functional agent comprising two or more functional groups, in which case the following items (A) through (C) are present: (A) the molecular weight average hydrodynamic radius of the crosslinkable reaction product in tetrahydrofuran (THF) solution at 30°C is less than about 30 nm at a weight average absolute molecular weight (Mw) of about 1,500,000 g / mol or less, as measured by gel permeation chromatography-multiangle light scattering detection-differential viscometry (GPC-MALS-DV); (B) the intrinsic viscosity of the crosslinked reaction product in THF solution at 30° C. is about 1.0 dL / g or less at a weight average absolute molecular weight (Mw) of about 1,500,000 g / mol or less, as measured by GPC-MALS-DV; and (C) The crosslinkable reaction product has a viscosity of about 110° C. and about 0.25 s when measured in a parallel plate rheometer. -1 at a shear rate of 90,000 cps to 7,000,000 cps after polymerization; Any one or more of the following applies:

[0110] Example

[0111] The present disclosure is further illustrated by the following examples, which should not be construed as limiting in any way, i.e., the specific features described in the following examples are merely illustrative and not limiting.

[0112] Example 1

[0113] A monomer mixture was prepared using 1.8 g of allyl methacrylate, 579.2 g of butyl acrylate, 10.3 g of Avery Dennison proprietary Monomer 001, 6.9 g of pentaerythritol tetrakis(3-mercaptopropionate), and 117.1 g of ethyl acetate, followed by a continuous nitrogen purging. Separately, an initiator solution was prepared using 0.096 g of t-amyl peroxypivalate and 159.7 g of ethyl acetate. 143.0 g of the above monomer mixture and 119.6 g of ethyl acetate were charged to a glass reactor equipped with a reflux condenser, thermocouple, nitrogen inlet, and a pitched turbine agitator set at 150 RPM. After 30 minutes of nitrogen sparging, the batch was heated to 80°C and a solution of 0.027 g of t-amyl peroxypivalate in 5.5 g of ethyl acetate was added. After 5 minutes, the remaining monomer mixture was added to the reactor at a rate of 4.8 g / min, while the initiator solution was simultaneously introduced into the reactor at a rate of 0.9 g / min. The batch temperature was maintained at 80-85°C. After the initiator solution was fed to the reactor, the batch was held at 80-85°C for 2 hours. The contents were then cooled to ambient temperature and discharged. The polymer was then characterized as described below.

[0114] Example 2

[0115] A monomer mixture was prepared using 25.0 g of acrylic acid, 469.8 g of butyl acrylate, 2.9 g of Avery Dennison proprietary Monomer 001, and 334.9 g of ethyl acetate and purged with a continuous nitrogen stream. Separately, an initiator solution was prepared by dissolving 0.096 g of t-amyl peroxypivalate in 40.0 g of ethyl acetate, then divided into eight equal aliquots. A glass reactor equipped with a reflux condenser, thermocouple, nitrogen inlet, and a pitched turbine agitator set at 150 RPM was charged with 166.5 g of the above monomer mixture, 119.6 g of ethyl acetate, and 2.3 g of dipentaerythritol hexakis(3-mercaptopropionate). After 30 minutes of nitrogen sparging, the batch was heated to 80°C and 0.027 g of t-amyl peroxypivalate dissolved in 5.5 g of ethyl acetate was added. After 5 minutes, the remaining monomer mixture was added to the reactor at a rate of 5.6 g / min, and aliquots of initiator solution were introduced into the reactor every 30 minutes thereafter. The batch temperature was maintained at 80-85°C. After all initiator solution aliquots had been delivered to the reactor, the batch was held at 80-85°C for 1 hour. The contents were then cooled to ambient temperature and discharged. The polymer was then subjected to characterization as described below.

[0116] Example 3

[0117] A monomer mixture was prepared using 25.0 g acrylic acid, 463.5 g butyl acrylate, 5.7 g Avery Dennison proprietary Monomer 001, and 264.2 g ethyl acetate and purged with a continuous nitrogen stream. Separately, an initiator solution was prepared using 0.45 g Vazo® 64 and 112.1 g ethyl acetate. A glass reactor equipped with a reflux condenser, thermocouple, nitrogen inlet, and a pitched turbine agitator set at 150 RPM was charged with 151.7 g of the above monomer mixture, 118.7 g ethyl acetate, 1.0 g allyl methacrylate, and 3.9 g pentaerythritol tetrakis(3-mercaptopropionate). After 30 minutes of nitrogen sparging, the batch was heated to 70°C and 0.47 g Vazo® 64 dissolved in 5.0 g ethyl acetate was added. After 5 minutes, the remaining monomer mixture was added to the reactor at a rate of 5.1 g / min, while the initiator solution was simultaneously introduced into the reactor at a rate of 0.75 g / min. The batch temperature was maintained at 80-85°C. After the initiator solution was fed to the reactor, the batch was held at 80-85°C for 2 hours. The contents were then cooled to ambient temperature and discharged. The polymer was then characterized as described below.

[0118] Example 4

[0119] A monomer mixture was prepared using 25.0 g of acrylic acid, 470.6 g of butyl acrylate, 2.9 g of Avery Dennison proprietary Monomer 001, and 215.8 g of ethyl acetate, then purged with a continuous nitrogen stream. Separately, an initiator solution was prepared using 0.096 g of t-amyl peroxypivalate and 159.7 g of ethyl acetate. A glass reactor equipped with a reflux condenser, thermocouple, nitrogen inlet, and a pitched turbine agitator set at 150 RPM was charged with 142.9 g of the above monomer mixture, 119.6 g of ethyl acetate, and 0.87 g of dipentaerythritol hexakis(3-mercaptopropionate). After 30 minutes of nitrogen sparging, the batch was heated to 80°C and 0.027 g of t-amyl peroxypivalate dissolved in 5.5 g of ethyl acetate was added. After 5 minutes, the remaining monomer mixture was added to the reactor at a rate of 4.8 g / min, while the initiator solution was simultaneously introduced into the reactor at a rate of 0.89 g / min. The batch temperature was maintained at 80-85°C. After the initiator solution was added to the reactor, the batch was held at 80-85°C for 2 hours. The contents were then cooled to room temperature and discharged from the reactor. The resulting polymer was characterized as described below.

[0120] control

[0121] H-505, an acrylic UV crosslinkable warm melt pressure sensitive adhesive, is commercially available from Avery Dennison Performance Polymers Division.

[0122] Characterization

[0123] Molecular weight distribution moment, weight average absolute molecular weight (Mw), polydispersity index (PDI=M w / M n , M wThe absolute molecular weight (M) and the radius of gyration of the polymer were measured using a Wyatt multi-angle light scattering (MALS) detector (Dawn) and a Viscostar differential viscometer detector connected to an Agilent 1260 GPC system equipped with an Agilent differential refractive index concentration detector. <rg>teeth, <rg>The MALS response was calculated using either the Zimm plot formalism if <40 nm or the Berry plot formalism if >40 nm.

[0124] Mark-Houwink-Sakurada formula, [η]=KM α Correlation was used to evaluate the relationship between intrinsic viscosity and absolute molecular weight (M), and the alpha (α) index was determined from regression analysis. Log-log Mark-Houwink-Sakurada plots were evaluated using linear regression correlation to observe uniform polymer chain structure. When a change in linear slope was observed, the distribution was divided into a high molecular weight (high M) and a low molecular weight (low M) linear region, and uniform branching ratio values ​​were observed.

[0125] Weight average branching ratio g' w to a linear analogue of the same molecular weight ([η] lin ) to the intrinsic viscosity of (non-linear) materials ([η] br ) to g' w =([η] br / [η] lin ) M Therefore, g' w When g' is 1.0, it is a linear polymer of similar chemical composition, and w is less than 1.0, which indicates a non-linear polymer. For experimental polymer samples that exceed the molecular weight of a linear reference polymer of similar monomer composition, a linear model extrapolation is used to determine [η] from the K and α coefficients determined for the linear reference polymer. lin was calculated.

[0126] Gel permeation chromatography (GPC) separations were performed using a set of three Agilent Mixed-C 5 micron, 7.5 × 300 mm columns in BHT-stabilized HPLC-grade tetrahydrofuran (THF) at 1.0 mL / min at 30 °C. Polymer samples were prepared at 5.0 mg / mL in THF and filtered through a 0.2 μm PTFE syringe filter before injection in 100 μL aliquots.

[0127] Unless otherwise noted, all samples are gel-free polymers, where a polymer gel is defined as a cross-linked polymer network that swells but is insoluble in solvents.

[0128] The Wyatt MALS instrument calibration factor was determined using 30 kDa narrow dispersity polystyrene. The refractive index increment (dn / dc) of the polymer was measured using a concentration series of neat copolymer in THF at 30 °C using the differential refractive index detector response to a known value of polystyrene standard (0.185 mL / g).

[0129] Rheological testing was performed using a DHR-2 rheometer (TA Instruments (Waters)) equipped with an 8 mm parallel plate fixture. Frequency sweeps were performed at various temperatures under a nitrogen atmosphere to generate a master curve at 140 °C using the time-temperature superposition principle. Any skilled / trained operator could perform the test. The Cox-Merz law was used to convert the complex viscosity versus frequency curve to a shear viscosity versus shear rate curve. The shear viscosity was measured at two different shear rates, 1 s -1 and 1000s -1 The viscosity of the sample at 1000 kJ / min was reported.

[0130] Table 1 below shows the molecular and physical properties of the objects prepared in Examples 1-4 compared to the control:

[0131] [Table 1]

[0132] M w = weight average absolute molecular weight of the whole sample, PDI = polydispersity index of the whole sample M w / M n , [η] = average intrinsic viscosity of the whole sample, Rh(v)w = weight average hydrodynamic radius of the whole sample.

[0133] The molecular properties of the individual polymer segments of high molecular weight (high M) and / or low molecular weight (low M) present in Examples 1-4 are shown in Table 2 below:

[0134] [Table 2]

[0135] M w = weight average absolute molecular weight, PDI = polydispersity index M w / M n , [η]=average intrinsic viscosity, Rh(v)w=weighted average hydrodynamic radius, alpha (α)=Mark-Houwink-Sakurada index, g' w =([η] br / [η] lin ) M , weight average intrinsic viscosity branching ratio.

[0136] The subject of Example 1 is composed of only one polymer segment like the control, whereas the subjects of Examples 2-4 are composed of at least two polymer segments with different molecular weights and properties.

[0137] Pressure Sensitive Adhesion Test

[0138] To evaluate pressure-sensitive adhesive performance, each polymer solution was applied to a 50 micron thick MYLAR® release liner at a dry coating weight of 55 g / m 2 (g / m²), dried at 120°C for 5 minutes, and UV-C dose 10-13mJ / cm 2 After crosslinking with , the film was transferred to a 2 mil thick MYLAR® film.

[0139] 180° peel adhesion values ​​were measured on stainless steel panels after a given hold time (i.e., 20 minutes or 24 hours) at a crosshead speed of 12 inches / minute (measured in lb / inch). Static shear values ​​(i.e., time to failure in minutes) were also measured on stainless steel panels at room temperature using a 1000 g load with a 1 inch x 1 inch contact area. All tests were conducted in a controlled environment at 22°C and 50% relative humidity.

[0140] Table 3 below shows the pressure sensitive adhesive performance (consisting of 180° peel adhesion and static shear) of the adhesive samples prepared in Examples 2, 3 and 4 compared to the control.

[0141] [Table 3] * Cohesive failure mode; ** Adhesive Failure Mode

[0142] The controls shown in Examples 2, 3 and 4, which have similar monomer compositions as the control, have balanced peel-shear performance and clearly outperform the control with respect to pressure sensitive adhesive.

[0143] The features, structures, or characteristics of the invention described throughout this specification may be combined in any suitable manner in one or more embodiments. For example, references throughout this specification to "one embodiment," "some embodiments," or similar expressions mean that the particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the invention. Thus, the appearances of "one embodiment," "some embodiments," "other embodiments," or similar expressions throughout this specification do not necessarily all refer to the same group of embodiments, but rather that the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0144] As set forth herein above, the subject matter of the present disclosure solves many of the problems associated with prior strategies, systems, and / or devices. However, it will be understood that various changes in the details, materials, and arrangements of the components and / or operations described and illustrated herein to illustrate the nature of the subject matter of the present disclosure may be made by those skilled in the art without departing from the spirit and scope of the claimed subject matter as expressed in the appended claims.< / rg> < / rg>

Claims

1. 1. A composition comprising a crosslinkable reaction product of a mixture, the mixture comprising: one or more monomers comprising a single polymerizable ethylenically unsaturated bond; one or more initiators; and a functional agent comprising one or more functional groups; and the one or more monomers are selected from the group consisting of (meth)acrylates, (meth)acrylamides, non-(meth)acrylates, and combinations thereof; the crosslinkable reaction product comprises a polymer composition selected from the group consisting of a first polymer, a second polymer, and combinations thereof; and When measured by gel permeation chromatography-multiangle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the polymer in tetrahydrofuran (THF) solution at 30°C, The following items (A) to (D): (A) the polymer has a weight average absolute molecular weight (Mw) in the range of about 10,000 to about 10,000,000 g / mol; (B) the polymer has a polydispersity index (PDI) of about 4.0 or less; (C) The polymer has the Mark-Houwink-Sakurada formula: [η] = KM α where [η] is the intrinsic viscosity of the polymer of absolute molecular weight M. an α value calculated according to the formula (I) is less than about 0.70; (D) The polymer has the formula: g' ｗ = [ηb] / [ηl], where [ηb] is the intrinsic viscosity of the polymer, and [ηl] is the intrinsic viscosity of a reference linear polymer measured under the same solvent and temperature conditions, both having the same molecular weight (M), the molecular weight being measured by GPC-MALS-DV. The weight average branching ratio g' is calculated according to ｗ is less than or equal to about 0.90; applies to the polymer.

2. The following items (A) to (I): (A) the polymer comprises a non-linear polymer; (B) the first polymer comprises a polymer selected from the group consisting of linear polymers, non-linear polymers, and combinations thereof; (C) the first polymer comprises a linear polymer; (D) the first polymer comprises a non-linear polymer; (E) the first polymer comprises a linear polymer and a non-linear polymer; (F) the first polymer and the second polymer are non-linear polymers; (G) the first polymer is less nonlinear than the second polymer; (H) the second polymer comprises a non-linear polymer; and (I) Nonlinear polymers are discrete molecules; 3. The composition of claim 2, wherein any one or more of the following applies:

3. as measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the first polymer and / or the second polymer in tetrahydrofuran (THF) solution at 30° C. The following items (A) to (F): (A) The first polymer has the Mark-Houwink-Sakurada formula: [η] = KM α where [η] is the intrinsic viscosity of the first polymer of absolute molecular weight M. an α value calculated according to is greater than about 0.50; (B) The first polymer is represented by the formula: g′ ｗ = [ηb] / [ηl], where [ηb] is the intrinsic viscosity of the first polymer, and [ηl] is the intrinsic viscosity of a reference linear polymer measured under the same solvent and temperature conditions, both having the same molecular weight (M), the molecular weight being measured by GPC-MALS-DV. The weight average branching ratio g' is calculated according to ｗ is greater than or equal to about 0.90; (C) The second polymer is a polymer having a molecular weight of 1.001 or more, the molecular weight of which is determined by the Mark-Houwink-Sakurada equation: [η] = KM α where [η] is the intrinsic viscosity of the polymer of absolute molecular weight M. an α value calculated according to the formula (I) is less than about 0.70; (D) The second polymer has the formula: g′ ｗ = [ηb] / [ηl], where [ηb] is the intrinsic viscosity of the second polymer, and [ηl] is the intrinsic viscosity of a reference linear polymer measured under the same solvent and temperature conditions, both having the same molecular weight (M), as measured by GPC-MALS-DV. The weight average branching ratio g' is calculated according to ｗ is less than or equal to about 0.90; (E) the α value of the first polymer is greater than the α value of the second polymer; and (F) The first polymer has a weight average branching ratio g′ equal to that of the second polymer. ｗ Weight average branching ratio g' greater than ｗ having applies to the first polymer and / or the second polymer.

4. as measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the first polymer and / or the second polymer in tetrahydrofuran (THF) solution at 30° C. The following items (A) to (R): (A) the first polymer has an α value of about 0.60 or greater and about 0.75 or less, and the second polymer has an α value of about 0.20 or greater and about 0.6 or less; (B) the first polymer has a weight average branching ratio g' of about 0.70 or more and about 1.00 or less; ｗ and the second polymer has a weight average branching ratio g' of about 0.20 or greater and about 0.70 or less. ｗ have a value; (C) the first polymer has an α value greater than about 0.70; (D) the first polymer has an α value greater than about 0.60; (E) the first polymer has an α value greater than about 0.50; (F) the first polymer has an α value of from about 0.70 to about 0.75; (G) the first polymer has an α value of about 0.60 to about 0.70; (H) the first polymer has an α value of about 0.50 to about 0.60; (I) The first polymer has a weight average branching ratio g′ of about 0.80 or greater. ｗ having (J) the second polymer has an α value of less than about 0.60; (K) the second polymer has an α value of less than about 0.50; (L) the second polymer has an α value of less than about 0.40; (M) the second polymer has an α value of less than about 0.30; (N) the second polymer has an α value of less than about 0.20; (O) the second polymer has an α value of about 0.60 to about 0.70; (P) the second polymer has an α value of about 0.50 to about 0.60; (Q) the second polymer has an α value of about 0.40 to about 0.30; and (R) The second polymer has an α value of about 0.30 to about 0.

20. The composition of any one of claims 1 to 3, wherein any one or more of the following applies to the first polymer and / or the second polymer.

5. The following items (A) to (E): (A) the polymer comprises a greater weight percent of a first polymer than a second polymer, based on the total weight of the polymer; (B) the polymer comprises 50% or more by weight of a first polymer; (C) the polymer comprises 60% or more by weight of a first polymer; (D) the polymer comprises 70% or more by weight of a first polymer; and (E) the polymer comprises 80% or more by weight of a first polymer; 5. The composition of claim 1, wherein any one or more of the following applies:

6. When measured by gel permeation chromatography-multiangle light scattering detection-differential viscometry (GPC-MALS-DV) on the polymer in tetrahydrofuran (THF) solution at 30°C: The following items (A) to (R): (A) the polymer has a weight average absolute molecular weight (Mw) greater than about 100,000 g / mol; (B) the polymer has a weight average absolute molecular weight (Mw) in the range of about 100,000 to about 10,000,000 g / mol; (C) the polymer has a weight average absolute molecular weight (Mw) greater than about 150,000 g / mol; (D) the polymer has a weight average absolute molecular weight (Mw) in the range of about 150,000 to about 10,000,000 g / mol; (E) the polymer has a weight average absolute molecular weight (Mw) greater than about 200,000 g / mol; (F) the polymer has a weight average absolute molecular weight (Mw) in the range of about 200,000 to about 10,000,000 g / mol; (G) the polymer has a weight average absolute molecular weight (Mw) greater than about 250,000 g / mol; (H) the polymer has a weight average absolute molecular weight (Mw) in the range of about 250,000 to about 10,000,000 g / mol; (I) the polymer has a weight average absolute molecular weight (Mw) greater than about 300,000 g / mol; (J) the polymer has a weight average absolute molecular weight (Mw) in the range of about 350,000 to about 10,000,000 g / mol; (K) the polymer has a weight average absolute molecular weight (Mw) greater than about 400,000 g / mol; (L) the polymer has a weight average absolute molecular weight (Mw) in the range of about 400,000 to about 10,000,000 g / mol; (M) the polymer has a weight average absolute molecular weight (Mw) greater than about 450,000 g / mol; (N) the polymer has a weight average absolute molecular weight (Mw) in the range of about 450,000 to about 10,000,000 g / mol; (O) the polymer has a weight average absolute molecular weight (Mw) greater than about 500,000 g / mol; (P) the polymer has a weight average absolute molecular weight (Mw) in the range of about 500,000 to about 10,000,000 g / mol; (Q) the polymer has a weight average absolute molecular weight (Mw) greater than about 550,000 g / mol; and The (R) polymer has a weight average absolute molecular weight (Mw) in the range of about 550,000 to about 10,000,000 g / mol; The composition of any one of claims 1 to 5, wherein any one or more of the following applies to the polymer:

7. When measured by gel permeation chromatography-multiangle light scattering detection-differential viscometry (GPC-MALS-DV) on the polymer in tetrahydrofuran (THF) solution at 30°C: The following items (A) to (I): (A) the polymer has a polydispersity index (PDI) of from about 1.1 to about 4.0 or less; (B) the polymer has a polydispersity index (PDI) of about 3.5 or less; (C) the polymer has a polydispersity index (PDI) of from about 1.1 to about 3.5 or less; (D) the polymer has a polydispersity index (PDI) of about 3.0 or less; (E) the polymer has a polydispersity index (PDI) of from about 1.1 to about 3.0 or less; (F) the polymer has a polydispersity index (PDI) of about 2.5 or less; (G) the polymer has a polydispersity index (PDI) of from about 1.1 to about 2.5 or less; (H) the polymer has a polydispersity index (PDI) of about 2.0 or less; and (I) the polymer has a polydispersity index (PDI) of from about 1.1 to about 2.0 or less; The composition of any one of claims 1 to 6, wherein any one or more of the following applies to the polymer:

8. as measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of the first polymer in tetrahydrofuran (THF) solution at 30° C. The following items (A) to (M): (A) the first polymer has a weight average absolute molecular weight (Mw) that is less than the weight average absolute molecular weight (Mw) of the second polymer; (B) the first polymer has a weight average absolute molecular weight (Mw) of greater than or equal to about 100,000 g / mol; (C) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 100,000 to about 5,000,000 g / mol; (D) the first polymer has a weight average absolute molecular weight (Mw) of about 200,000 g / mol or greater; (E) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 200,000 to about 5,000,000 g / mol; (F) the first polymer has a weight average absolute molecular weight (Mw) of greater than or equal to about 400,000 g / mol; (G) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 400,000 to about 5,000,000 g / mol; (H) the first polymer has a weight average absolute molecular weight (Mw) of greater than or equal to about 500,000 g / mol; (I) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 500,000 to about 5,000,000 g / mol; (J) the first polymer has a weight average absolute molecular weight (Mw) of greater than or equal to about 700,000 g / mol; (K) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 700,000 to about 5,000,000 g / mol; (L) the first polymer has a weight average absolute molecular weight (Mw) of about 1,000,000 g / mol or greater; and (M) the first polymer has a weight average absolute molecular weight (Mw) in the range of about 1,000,000 to about 5,000,000 g / mol; The composition of any one of claims 1 to 7, wherein any one or more of the following applies to the first polymer:

9. as measured by gel permeation chromatography-multi-angle light scattering detection-differential viscometry (GPC-MALS-DV) in the presence of a second polymer in tetrahydrofuran (THF) solution at 30° C. The following items (A) to (S): (A) the second polymer has a weight average absolute molecular weight (Mw) greater than the weight average absolute molecular weight (Mw) of the polymer; (B) the second polymer has a weight average absolute molecular weight (Mw) greater than about 300,000 g / mol; (C) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 300,000 to about 30,000,000 g / mol; (D) the second polymer has a weight average absolute molecular weight (Mw) greater than about 600,000 g / mol; (E) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 600,000 to about 30,000,000 g / mol; (F) the second polymer has a weight average absolute molecular weight (Mw) greater than about 900,000 g / mol; (G) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 900,000 to about 30,000,000 g / mol; (H) the second polymer has a weight average absolute molecular weight (Mw) greater than about 1,200,000 g / mol; (I) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 1,200,000 to about 30,000,000 g / mol; (J) the second polymer has a weight average absolute molecular weight (Mw) greater than about 1,500,000 g / mol; (K) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 1,500,000 to about 30,000,000 g / mol; (L) the second polymer has a weight average absolute molecular weight (Mw) greater than about 3,000,000 g / mol; (M) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 3,000,000 to about 30,000,000 g / mol; (N) the second polymer has a weight average absolute molecular weight (Mw) greater than about 5,000,000 g / mol; (O) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 5,000,000 to about 30,000,000 g / mol; (P) the second polymer has a weight average absolute molecular weight (Mw) greater than about 6,000,000 g / mol; (Q) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 6,000,000 to about 30,000,000 g / mol; (R) the second polymer has a weight average absolute molecular weight (Mw) greater than about 9,000,000 g / mol; and (S) the second polymer has a weight average absolute molecular weight (Mw) in the range of about 9,000,000 to about 30,000,000 g / mol; The composition of any of claims 1 to 8, wherein any one or more of the following applies to the second polymer:

10. When measured by gel permeation chromatography-multiangle light scattering detection-differential viscometry (GPC-MALS-DV) on the polymer in tetrahydrofuran (THF) solution at 30°C: The following items (A) to (I): (A) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 4.0 or less; (B) the first and / or second polymer has a polydispersity index (PDI) of about 3.5 or less; (C) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 3.5 or less; (D) the first and / or second polymer has a polydispersity index (PDI) of about 3.0 or less; (E) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 3.0 or less; (F) the first and / or second polymer has a polydispersity index (PDI) of about 2.5 or less; (G) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 2.5 or less; (H) the first and / or second polymer has a polydispersity index (PDI) of about 2.0 or less; and (I) the first and / or second polymer has a polydispersity index (PDI) of from about 1.1 to about 2.0 or less; The composition of any one of claims 1 to 9, wherein any one or more of the following applies to the polymer:

11. When measured on a parallel plate rheometer for the polymer after polymerization at a temperature of about 140°C: The following items (A) to (W): (A) The polymer is about 1.0 s －１ having a first melt viscosity after polymerization of about 30,000 cps (30 Pa s) or greater at a shear rate of (B) The polymer is about 1.0 s －１ having a first melt viscosity after polymerization of greater than or equal to about 40,000 cps (40 Pa s) at a shear rate of (C) The polymer is about 1.0 s －１ having a first melt viscosity after polymerization of greater than or equal to about 50,000 cps (50 Pa s) at a shear rate of (D) The polymer has a viscosity of about 1.0 s －１ having a first melt viscosity after polymerization of greater than or equal to about 60,000 cps (60 Pa s) at a shear rate of (E) The polymer has a viscosity of about 1.0 s －１ having a first melt viscosity after polymerization of greater than or equal to about 70,000 cps (70 Pa s) at a shear rate of (F) The polymer is about 1.0 s －１ having a first melt viscosity after polymerization of greater than or equal to about 80,000 cps (80 Pa s) at a shear rate of (G) The polymer is about 1.0 s －１ having a first melt viscosity after polymerization of about 90,000 cps (90 Pa s) or greater at a shear rate of (H) The polymer is about 1.0 s －１ having a first melt viscosity after polymerization of about 100,000 cps (100 Pa s) or greater at a shear rate of (I) The polymer has a viscosity of about 1.0 s －１ having a first melt viscosity after polymerization of greater than or equal to about 200,000 cps (200 Pa s) at a shear rate of (J) The polymer is －１ having a second melt viscosity after polymerization of about 1,000 cps (1 Pa s) or more at a shear rate of (K) Polymer is about 1000 s －１ having a second melt viscosity after polymerization of about 2,000 cps (2 Pa s) or more at a shear rate of (L) polymer is about 1000 s －１ having a second melt viscosity after polymerization of about 5,000 cps (5 Pa s) or more at a shear rate of (M) polymer is about 1000 s －１ having a second melt viscosity after polymerization of about 10,000 cps (10 Pa s) or greater at a shear rate of (N) Polymer is about 1000 s －１ having a second melt viscosity after polymerization of about 15,000 cps (15 Pa s) or greater at a shear rate of (O) The polymer is －１ having a second melt viscosity after polymerization of about 20,000 cps (20 Pa s) or greater at a shear rate of (P) Polymer is about 1000 s －１ having a second melt viscosity after polymerization of about 30,000 cps (30 Pa s) or greater at a shear rate of (Q) The polymer is about 1000 s －１ having a second melt viscosity after polymerization of about 40,000 cps (40 Pa s) or greater at a shear rate of (R) polymer is approximately 1000s －１ having a second melt viscosity after polymerization of about 50,000 cps (50 Pa s) or greater at a shear rate of (S) polymer is about 1.0s －１ and a first melt viscosity after polymerization in the range of about 30,000 cps (30 Pa s) to about 4,000,000 cps (4,000 Pa s) at a shear rate of about 1,000 s. －１ a second melt viscosity in the range of about 1,000 cps (1 Pa·s) to about 200,000 cps (200 Pa·s) at a shear rate of (T) The polymer is about 1.0 s －１ and a first melt viscosity after polymerization in the range of about 30,000 cps (30 Pa s) to about 4,000,000 cps (4,000 Pa s) at a shear rate of about 1,000 s. －１ a second melt viscosity in the range of about 15,000 cps (15 Pa·s) to about 200,000 cps (200 Pa·s) at a shear rate of (U) Polymer is about 1.0 s －１ and a first melt viscosity after polymerization in the range of about 30,000 cps (30 Pa s) to about 4,000,000 cps (4,000 Pa s) at a shear rate of about 1,000 s. －１ a second melt viscosity in the range of about 40,000 cps (40 Pa·s) to about 200,000 cps (200 Pa·s) at a shear rate of (V) The polymer has a viscosity of about 1.0 s －１ and a first melt viscosity after polymerization in the range of about 100,000 cps (100 Pa s) to about 4,000,000 cps (4,000 Pa s) at a shear rate of about 1000 s －１ a second melt viscosity in the range of about 15,000 cps (15 Pa s) to about 200,000 cps (200 Pa s) at a shear rate of (W) polymer is about 1.0 s －１ and a first melt viscosity after polymerization in the range of about 100,000 cps (100 Pa s) to about 4,000,000 cps (4,000 Pa s) at a shear rate of about 1000 s －１ a second melt viscosity in the range of about 40,000 cps (40 Pa·s) to about 200,000 cps (200 Pa·s) at a shear rate of The composition of any one of claims 1 to 10, wherein any one or more of the following applies to the polymer after polymerization:

12. The mixture is one or more monomers comprising from about 80 to about 99 weight percent of a single polymerizable ethylenically unsaturated bond; about 0.001 to about 5 wt. % of one or more initiators; and about 0.001 to about 5 wt. % of a functional agent; and The composition of any of claims 1 to 11, wherein the weight percentages of the components add up to 100% based on the total weight of the polymer.

13. 13. The composition of any of claims 1 to 12, wherein the one or more monomers are selected from the group consisting of acrylic acid, acrylates comprising a C1 to about C20 alkyl, aryl, aralkyl, or cyclic acrylate, acrylamides comprising a C1 to about C20 alkyl, aryl, aralkyl, or cyclic acrylamide, methacrylic acid, methacrylates comprising a C1 to about C20 alkyl, aryl, aralkyl, or cyclic methacrylate, methacrylamides comprising a C1 to about C20 alkyl, aryl, aralkyl, or cyclic methacrylamide, vinyl monomers, olefins, vinyl aromatics, (meth)acrylated urethanes, (meth)acrylated carbonates, (meth)acrylated esters, (meth)acrylated ethers, vinyl esters, vinyl pyrrolidone, styrene, and combinations thereof.

14. The following items (A) to (G): (A) one or more monomer conversions are at least about 90%; (B) the one or more monomers further comprise one or more crosslinkable functional groups, the crosslinkable functional groups selected from the group consisting of actinically active functional groups, self-reactive functional groups, reactive functional groups, and combinations thereof; (C) the actinically active functional group is activatable using actinic or electron beam radiation; (D) the actinically active functional group is selected from the group consisting of benzophenone, double bond, and combinations thereof; (E) the actinically active functional group is selected from the group consisting of acetophenone, acetophenone derivatives, benzophenone, benzophenone derivatives, anthraquinone, anthraquinone derivatives, benzil, benzil derivatives, thioxanthone, thioxanthone derivatives, xanthone, xanthone derivatives, benzoin ethers, benzoin ether derivatives, α-ketol, α-ketol derivatives, and combinations thereof; (F) the reactive functional group is selected from the group consisting of hydroxyl, carboxyl, carbonyl, carbonate ester, isocyanate, epoxy, vinyl, amine, amide, imide, anhydride, mercapto (thiol), acid, acrylamide, acetoacetyl group, alkoxymethylol, cyclic ether group, and combinations thereof; and (G) the self-reactive functional group is selected from the group consisting of silane, silyl, anhydride, epoxy, alkoxy-methylol, and cyclic ether; 14. The composition of any one of claims 1 to 13, wherein any one or more of the following applies:

15. 15. The composition of any of claims 1 to 14, wherein the one or more initiators are selected from the group consisting of actinically activated initiators, electron beam radiation activated initiators, thermally activated initiators, redox initiators, electrochemical initiators, and combinations thereof.

16. the one or more initiators comprise at least one polymerization initiator and at least one cross-linking initiator; The following items (A) to (N): (A) Both the polymerization initiator and the crosslinking initiator are actinically activated initiators; (B) the polymerization initiator is activatable at a first activation wavelength; (C) the crosslinking initiator is activatable at a second activation wavelength; (D) the polymerization initiator is selectively activatable in the presence of the crosslinking initiator without activating the crosslinking initiator; (E) the polymerization initiator is selectively activatable in the presence of the crosslinking initiator without activating the crosslinking initiator and without the use of an optical filter; (F) the polymerization initiator can be selectively activated in the presence of the crosslinking initiator without activating the crosslinking initiator and using an optical filter; (G) the optical filter is selected from the group consisting of an absorptive filter, a dichroic filter, a polychroic filter, a notch filter, a short-pass filter, a long-pass filter, a band-pass filter, a multiple-band filter (e.g., a triple-band filter), and combinations thereof; (H) the optical filter is selected from a polymer layer, a lens, a film, and combinations thereof; (I) the polymerization initiator is substantially non-photoactive at the activation wavelength of the crosslinking initiator; (J) the crosslinking initiator is substantially non-photoactive at the activation wavelength of the polymerization initiator; (K) at least one of the polymerization initiator and the crosslinking initiator comprises a polymerizable monomer containing a photoinitiator moiety; (L) the polymerization initiator is a thermally activated initiator and the crosslinking initiator is an actinically activated initiator; (M) the polymerization initiator is an actinically activated initiator, and the crosslinking initiator is at least one of a thermally activated initiator and an actinically activated initiator; and (N) the polymerization initiator is at least one of a thermally activated initiator and an actinically activated initiator, and the crosslinking initiator is at least one of a thermally activated initiator and an actinically activated initiator; 16. The composition of any one of claims 1 to 15, wherein any one or more of the following applies:

17. The following items (A) to (K): (A) Functional group agent (a) a multifunctional initiator; (b) a multifunctional chain transfer agent; (c) a polyfunctional monomer; (d) a linear polymer or oligomer comprising one or more multifunctional initiators chemically bonded onto the polymer or oligomer backbone; and (e) Linear polymers or linear oligomers comprising / having / including two or more monofunctional initiators chemically bonded onto the polymer or oligomer backbone, and combinations thereof. selected from the group consisting of: (B) the functional group agent comprises a multifunctional chain transfer agent; (C) the functional agent comprises two or more functional groups; (D) the functional agent comprises three or more functional groups; (E) Other than the functional group agent, the mixture does not contain any other monomers comprising two or more polymerizable ethylenically unsaturated bonds; (F) Multifunctional chain transfer agents comprise two or more functional groups, the functional groups having the same or different reactivities; (G) polyfunctional chain transfer agents comprise a polyvalent mercaptan core comprising three or more thiol (SH) groups, the thiol groups having the same or different reactivities; (H) the functional group agent comprises a polyvalent or polyfunctional atom or molecule; (I) The functional group agent comprises a polyhydric or polyfunctional mercaptan; (J) the functional group agent comprises a derivative of a thiocarboxylic acid; and (K) the functional group agent is derived from a polythiocarboxylic acid selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), dipentaerythritol hexakis(3-mercaptopropionate) (DPMP), trimethylolpropane tris(3-mercaptopropionate) (TMMP), and tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate (TEMPIC), and combinations thereof; The composition according to any one of claims 1 to 16, wherein any one or more of the following applies: 。

18. The composition of any preceding claim, wherein the mixture further comprises a coupling agent.

19. The following items (A) to (M): (A) the mixture comprises less than 0.5 wt. % of a coupling agent; (B) the mixture comprises less than 0.3 wt. % of a coupling agent; (C) the mixture comprises about 0.001 to about 0.29 weight percent of a coupling agent; (D) the coupling agent comprises a monomer; (E) the coupling agent comprises at least one polymerizable ethylenically unsaturated bond; (F) the coupling agent comprises two or more polymerizable ethylenically unsaturated bonds; (G) the coupling agent is incapable of participating in a free radical polymerization reaction; (H) the coupling agent comprises a functional group capable of reacting under non-free radical conditions in a condensation reaction; (I) The coupling agent is capable of participating in a free radical process; (J) the coupling agent comprises a cationically polymerizable group; (K) the coupling agent comprises a vinyl ether group; (L) the coupling agent is capable of undergoing a thiol-ene reaction; Examples of the coupling agent (M) include aliphatic divinyl compounds such as divinyl ether, diisocyanate, polyfunctional (meth)acrylate, bifunctional (meth)acrylate, hexa-1,5-diene, hepta-1,6-diene, ethylene glycol dimethacrylate, methylene di(meth)acrylate, and ethylenedivinylurea; aromatic divinyl compounds such as divinylbenzene, methyldivinylbenzene, divinyltoluene, divinylbiphenyl, diallyl phthalate, and divinylnaphthalene; polyhydric ethylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate; polyhydric propane compounds such as propylene glycol di(meth)acrylate and dipropylene glycol di(meth)acrylate. propylene glycol di(meth)acrylate; di(meth)acrylate compounds such as 1,2-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-methyl-1,8-octanediol (meth)acrylate, and 1,4-cyclohexanediol dimethacrylate; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate and ethylene glycol dimethacrylate; and divinyl compounds such as divinyl ether, divinyl sulfite, divinyl sulfone, and N,N'-methylenebisacrylamide; 19. The composition of claim 18, wherein any one or more of the following applies:

20. The composition of any of claims 1 to 19, wherein the mixture further comprises a multifunctional agent.

21. The following items (A) to (N): (A) the mixture comprises less than 0.5 wt. % of a multifunctional agent; (B) the mixture comprises less than 0.3 wt. % of a multifunctional agent; (C) the mixture comprises 0.001 to less than 0.3 weight percent of a multifunctional agent; (D) The polyfunctional agent is a monomer; (E) The multifunctional agent is chemically bonded to the backbone of the polymer; (F) the polyfunctional agent comprises at least one ethylenically unsaturated bond; (G) the polyfunctional agent comprises two or more ethylenically unsaturated bonds; (H) the multifunctional agent comprises at least one of ethylenic unsaturation and acrylate unsaturation; (I) the polyfunctional agent comprises a functional group capable of reacting under non-free radical conditions in a condensation reaction; (J) the multifunctional agent is capable of undergoing a thiol-ene reaction; (K) The polyfunctional agent comprises at least one radically polymerizable group and at least one cationically polymerizable group in one molecule; (L) The polyfunctional agent contains at least one (meth)acryloyl group and at least one vinyl ether group in one molecule; The (M) polyfunctional agent is represented by the following formula (I): In the formula, R １ is hydrogen; aliphatic C １～６ alkyl; and C １～６ cycloalkyl; R ２ is C ２～２０ Alkylene; C ２～２０ a hydrocarbon diradical; and a polyalkylene oxide; and R ３ is selected from hydrogen and methyl; and (N) The multifunctional agent is selected from the group consisting of multifunctional (meth)acrylates, allyl (meth)acrylates, vinyl ether (meth)acrylates, α-olefin maleic anhydrides (AOMA), 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA), 2-(2′-vinyloxyethoxy)ethyl methacrylate (VEEM), 2-vinyloxyethyl acrylate, 2-vinyloxyethyl methacrylate, 2-(2′-prop-1-enyloxyethoxy)ethyl methacrylate, 2-(2′-prop-1-enyloxyethoxy)ethyl acrylate, and combinations thereof; 21. The composition of claim 20, wherein any one or more of the following applies:

22. The following items (A) to (F): (A) the mixture further comprises a non-reactive carrier; (B) the mixture does not include a non-reactive carrier; (C) A non-reactive carrier does not react with the functional groups of the components of the mixture; (D) the non-reactive carrier is selected from the group consisting of organic solvents, water, and combinations thereof; (E) the organic solvent is selected from the group consisting of aromatic hydrocarbons, alkyl esters, cycloaliphatic hydrocarbons, aliphatic hydrocarbons, ketones, amines, amides, esters, ethers, aliphatic esters, alcohols, nitrated hydrocarbons, unsaturated hydrocarbons, chlorinated hydrocarbons, and combinations thereof; and (F) the mixture has a pre-polymerization viscosity of about 2 cps to about 50 cps at room temperature; 22. The composition of any one of claims 1 to 21, wherein any one or more of the following applies:

23. The following items (A) to (B): (A) the composition further comprises a ring-opening monomer selected from the group consisting of an epoxy, an oxetane, an anhydride, a lactone, a lactam, a cyclic ether, and a cyclic siloxane, and combinations thereof, and a cationically polymerizable monomer selected from the group consisting of an epoxy-containing material, an alkyl vinyl ether, a cyclic ether, a styrene, a divinylbenzene, a vinyl toluene, an N-vinyl compound, a cyanate ester, a 1-alkyl olefin (α-olefin), a lactam, and a cyclic acetal, and combinations thereof; and (B) the composition further comprises at least one component selected from the group consisting of pigments, tackifiers, plasticizers, fillers, diluents, suppressors, and combinations thereof; 23. The composition of any one of claims 1 to 22, wherein any one or more of the following applies:

24. The following items (A) to (G): (A) The reaction is a solvent polymerization reaction; (B) The reaction is a non-solution process; (C) The reaction is an emulsion polymerization reaction; (D) The reaction is a bulk polymerization reaction; (E) The reaction is a suspension polymerization reaction; (F) The reaction is a one-step process. (G) The reaction is a two-step or more step process; 24. The composition of any one of claims 1 to 23, wherein any one or more of the following applies:

25. The following items (A) to (I): (A) The polymer is soluble in a non-reactive carrier; (B) the conversion of monomer to polymer is greater than 90%; (C) the polymer is 100% solids; (D) the polymer is not gelled (gel-free); (E) the polymer has a unimodal molecular weight distribution as measured by GPC-MALS-DV; (F) the polymer has a multimodal molecular weight distribution as measured by GPC-MALS-DV; (G) the polymer has a glass transition temperature (Tg) of from about 100°C to about -115°C as measured by differential scanning calorimetry (DSC); (H) the polymer has a single glass transition temperature (Tg) in the range of about 100°C to about -115°C as measured by differential scanning calorimetry (DSC); and (I) the polymer has two or more glass transition temperatures (Tg) within the range of about 100°C to about -115°C, as measured by differential scanning calorimetry (DSC); 25. The composition of any one of claims 1 to 24, wherein any one or more of the following applies:

26. The composition of any one of claims 1 to 25, wherein the reaction is a free radical polymerization reaction.

27. The polymer, when at least partially crosslinked, has the following properties (A) to (G): (A) the polymer is at least partially crosslinked to form an adhesive; (B) the polymer is at least partially crosslinked and has a plateau shear modulus of 10 at 25° C. and 1 rad / sec as measured by dynamic mechanical analysis (DMA). ４ ~10 ７ dynes / cm ２ forming an adhesive which is (C) the polymer is at least partially crosslinked to form a pressure sensitive adhesive; (D) the at least partial crosslinking is achieved using at least one of actinic radiation, electron beam radiation, heat, moisture, or metal-based ionic crosslinking; (E) at least partial crosslinking of the polymer is effected by heating the composition; (F) at least partial crosslinking of the polymer is achieved via metal-based ionic crosslinking; and (G) at least partial crosslinking of the polymer is effected by exposing the composition to actinic or electron beam radiation; 27. The composition of any one of claims 1 to 26, wherein any one or more of the following applies:

28. A pressure sensitive adhesive comprising a polymer according to any one of claims 1 to 27.

29. 28. An article comprising the adhesive of claim 27, The article further comprises a substrate defining a surface; An article wherein the adhesive is directly applicable to at least a portion of the surface of the substrate and does not require a primer to be disposed between the adhesive and the substrate.

30. the substrate is heat sensitive at temperatures above about 110°C; the substrate is selected from the group consisting of polypropylene, polyethylene, and vinyl; and 30. The article of claim 29, wherein the polyethylene is selected from the group consisting of linear density polyethylene (LDPE), linear low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHMWPE), and combinations thereof.

31. 28. An article comprising the adhesive of claim 27, The article further comprises a substrate defining a surface; The adhesive can be coated onto a carrier or release liner before being transferred to the substrate; and The article, wherein the carrier is selected from the group consisting of silicone coated paper, polyethylene film, polyester film, glassine paper, polycoated kraft paper, fluoropolymer film, release coated textiles, thermoplastic film, polypropylene film, release coated foil, and polyvinyl chloride (PVC) film.

32. 1. A method of forming a composition comprising a crosslinkable polymer, comprising: providing a mixture according to any one of claims 1 to 26; polymerizing the mixture via a free radical polymerization reaction to form a polymer according to any one of claims 1 to 26; The method comprising:

33. 33. The method of claim 32, wherein polymerizing comprises heating the mixture.

34. 33. The method of claim 32, wherein polymerizing comprises exposing the mixture to actinic or electron beam radiation.

35. The method of any of claims 32 to 34, further comprising the step of cross-linking the polymer to form the adhesive.

36. The adhesive exhibits a 10 rad / sec viscosity at 25°C and 1 rad / sec as measured by dynamic mechanical analysis (DMA). ４ ~10 ７ dynes / cm ２ 36. The method of claim 35, wherein the plateau shear modulus is

37. 37. The method of claim 35 or 36, wherein the adhesive is a pressure sensitive adhesive.

38. The method of any of claims 35 to 37, wherein the crosslinking is activatable by at least one of actinic radiation, electron beam radiation, heat, moisture, or metal-based ionic crosslinking.

39. The method of any of claims 32 to 38, wherein the polymerization of the mixture to form the polymer is carried out in one step.

40. The method of any of claims 32 to 38, wherein the polymerization of the mixture to form the polymer is carried out in two or more stages.

41. A polymer blend comprising a first polymer and a second polymer according to any one of claims 1 to 26.

42. 1. A composition comprising a crosslinkable reaction product of a mixture comprising: one or more monomers comprising a single polymerizable ethylenically unsaturated bond; one or more initiators; and a functional agent comprising two or more functional groups; and the one or more monomers are selected from the group consisting of (meth)acrylates, (meth)acrylamides, non-(meth)acrylates, and combinations thereof; The following items (A) to (C): (A) the molecular weight average hydrodynamic radius of the crosslinkable reaction product in tetrahydrofuran (THF) solution at 30° C. is less than about 30 nm at a weight average absolute molecular weight (Mw) of about 1,500,000 g / mol or less, as measured by gel permeation chromatography-multiangle light scattering detection-differential viscometry (GPC-MALS-DV); (B) the intrinsic viscosity of the crosslinked reaction product in THF solution at 30° C. is about 1.0 dL / g or less at a weight average absolute molecular weight (Mw) of about 1,500,000 g / mol or less, as measured by GPC-MALS-DV; and (C) The crosslinkable reaction product has a viscosity of about 110° C. and about 0.25 s when measured with a parallel plate rheometer. －１ having a post-polymerization melt viscosity in the range of 90,000 cps to 7,000,000 cps at a shear rate of A composition according to any one or more of the following:

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