Catechol-urethane compositions and methods for use in wet-bonding

Abstract

The present invention relates to thin layers comprising catechol containing polymer or oligomer, which demonstrate improved adhesion for wet bonding.

Description

CATECHOL-URETHANE COMPOSITIONS AND METHODS FOR USE IN WET-BONDINGTECHNICAL FIELD

[0001] The present invention relates to thin layers comprising catechol containing polymer or oligomer, which demonstrate improved adhesion for wet bonding.CROSS REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 593,613, filed October 27, 2023, which is incorporated by reference herein in its entirety for any and all purposes.BACKGROUND

[0003] Underwater / wet adhesion is a critical problem to overcome in fields of engineering (e.g., construction), biomedical (e.g., tissue adhesives), environmental (e.g., coral restoration), and many more. Current synthetic adhesives fail in the presence of water due to the disruption of contact between the adhesive and adherend substrate.

[0004] Cross linking agents are readily used in polyurethane adhesive systems. For example, a rotaxane consisting of a polyhydroxy aliphatic compound has been shown in the art. The rotaxane being used most possess at least four active hydrogen groups.

[0005] A similar trend can be seen when reviewing the current patent landscape on adhesion promoters in polyurethane adhesive systems. Isocyanate has been used as a prepolymer having active hydrogens that is reacted with two or more compounds having active hydrogen sites. Typical polyurethane catalysts are either metallic (e.g., mercury, tin, zinc) or amines (e.g., triethylenediamine).

[0006] There is a long felt need for improved adhesive compositions for wet bonding for use in under water applications that offer both short cure times and strong bond strength. The present disclosure addresses this need.SUMMARY

[0007] In meeting the long-felt needs described above, the present disclosure provides a polymeric layer comprising a catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi-quinone and / or as a quinone without the presence of a primary amine or a secondary amine; and wherein the polymeric layer optionally comprises at least one of: a) a reactive species separate from the catechol containing polymer or oligomer; and b) a catalyst, co-catalyst or an accelerator. The present disclosure is also directed to methods of using the polymeric layer comprising the catechol containing polymer or oligomer as an adhesive with various materials. In an aspect, the catechol containing polymer or oligomer is poly-catechol styrene (PCS). The composition of the present disclosure combines biomimetic mussel polymers and urethane chemistry to create a long- lasting, easy to use underwater bonding agent. Mussel polymers are catechol containing polymers similar to proteins that mussels use to bind to the ocean floor. By adding the catechol functionality to the urethane adhesive system through poly(catechol-co-styrene), a robust two-part adhesive system is created that allows for underwater bonding in a variety of applications.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] In the drawings, which are not necessarily drawn to scale, like numerals can describe similar components in different views. Like numerals having different letter suffixes can represent different instances of similar components. The drawings illustrate generally, by way of example, but not by way of limitation, various aspects discussed in the present document. In the drawings:

[0009] FIG. 1 depicts a schematic of the layers and layered articles described herein. FIG. 1 A depicts an embodiment that includes a second layer of the inventive formulation. FIG. IB depicts an embodiment that does not include a second layer of the inventive formulation.

[0010] FIG. 2 depicts a graph showing the effect of PCS concentration and molecular weight (MW) on handling time of the composition of the present disclosure.

[0011] FIG. 3 depicts an image of a 15 lb deadweight peel test performed for the duration of 3 weeks using various formulations of the composition of the present disclosure.

[0012] FIG. 4 depicts a graph showing peel test results performed using various formulations of the composition of the present disclosure adhering a VERSATHANE™ substrate to hy coted steel.

[0013] FIG. 5 depicts a graph showing peel strength results of the composition of the present disclosure adhering VERSATHANE™ to hycoted steel.

[0014] FIG. 6 depicts time-stamped test strips used to determine preferred handling time for optimal performance. A 95% / 5% formulation with 5 mL MEK was used. A handling time of 40 minutes is targeted.DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

[0015] The present disclosure provides a polymeric layer containing a moisture-cure polyurethane and a catechol containing polymer or oligomer adhesive composition.

[0016] In the present disclosure the singular forms “a,” “an,” and “the” include the plural reference, and reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to “a material” is a reference to at least one of such materials and equivalents thereof known to those skilled in the art, and so forth.

[0017] When a value is expressed as an approximation by use of the descriptor “about” or “substantially” it will be understood that the particular value forms another embodiment. In general, use of the term “about” or “substantially” indicates approximations that can vary depending on the desired properties sought to be obtained by the disclosed subject matter and is to be interpreted in the specific context in which it is used, based on its function. The person skilled in the art will be able to interpret this as a matter of routine. In some cases, the number of significant figures used for a particular value may be one non-limiting method of determining the extent of the word “about” or “substantially.” In other cases, the gradations used in a series of values may be used to determine the intended range available to the term “about” or “substantially” for each value. Where present, all ranges are inclusive and combinable. That is, references to values stated in ranges include every value within that range.

[0018] When a list is presented, unless stated otherwise, it is to be understood that each individual element of that list and every combination of that list is to be interpreted as a separate embodiment. For example, a list of embodiments presented as “A, B, or C” is to beinterpreted as including the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,” or “A, B, or C ”

[0019] It is to be appreciated that certain features of the disclosure which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. That is, unless obviously incompatible or excluded, each individual embodiment is deemed to be combinable with any other embodiments and such a combination is considered to be another embodiment. Conversely, various features of the disclosure that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as “solely,” “only” and the like in connection with the recitation of claim elements, or use of a “negative” limitation. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step may also be considered an independent embodiment in itself.

[0020] As used herein, the term “handling time” refers to the time that the user can handle the mixed adhesive before it is no longer able to be smoothly applied.

[0021] As used herein, the term “settling time” refers to the time it takes for the applied adhesive to cure enough to prevent movement of the adhered material.

[0022] As used herein, the term “cure time” refers to the time it takes for the applied adhesive to have thorough cure.

[0023] In an aspect, the disclosure is directed to a polymeric layer comprising a catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi-quinone and / or as a quinone without the presence of a primary amine or a secondary amine; and wherein the polymeric layer optionally comprises at least one of: a) a reactive species separate from the catechol containing polymer or oligomer; and b) a catalyst, cocatalyst or an accelerator.

[0024] In some embodiments, the polymeric layer comprises the catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of a primary amine or a secondary amine.

[0025] In some embodiments, the polymeric layer comprises the catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of a primary amine or a secondary amine; and also comprises the reactive species separate from the catechol containing polymer or oligomer.

[0026] In some embodiments, the polymeric layer comprises the catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of a primary amine or a secondary amine. In some embodiments, the polymeric layer comprises the catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of a primary amine or a secondary amine; and also comprises the catalyst, co-catalyst or an accelerator.

[0027] In some embodiments, the polymeric layer comprises the catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of a primary amine or a secondary amine. In some embodiments, the polymeric layer comprises the catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of a primary amine or a secondary amine; and also comprises both the reactive species separate from the catechol containing polymer or oligomer and the catalyst, co-catalyst or an accelerator.

[0028] FIG. 1 depicts a general schematic of the polymeric layer 20 comprising the catechol containing polymer or oligomer and a layered article 100 comprising the polymer layer described herein. The layered article 100 may comprise a substrate 10 which the polymeric layer 20 is disposed on and in contact with. The layered article 100 may also comprise a polymer matrix 30 disposed on the polymeric layer 20 and in contact with the polymeric layer 20. The layered article 100 may also comprise a second polymeric layer comprising the catechol containing polymer or oligomer 40 disposed on and in contact with polymer matrix 30. The layered article 100 may also comprise a second substrate 50 disposed on and in contact with the second polymeric layer 40.

[0029] In some embodiments, the catechol containing polymer or oligomer in the polymeric layer 20 is oligomeric. In some embodiments, the catechol containing polymer or oligomer in the polymeric layer 20 is polymeric.

[0030] In an aspect, the polymeric layer 20 comprises the reactive species separate from the catechol containing polymer or oligomer. In an aspect, the reactive species is a urethane component, an epoxy resin, an acrylate monomer or oligomer, a methacrylate monomer or oligomer, a silane, or a combination thereof.

[0031] In some embodiments, the reactive species separate from the catechol containing polymer or oligomer is a urethane component. In some embodiments, the urethanecomponent is a polyol or an organic compound containing multiple hydroxyl groups; and wherein the urethane is linear or branched.

[0032] In some embodiments, the urethane component is 1,6-hexanediol, glycerol, Stepanpol PDC-279® or polycaprolactone triol. In some embodiments, the urethane component is 1,6-hexanediol. In some embodiments, the urethane component is glycerol. In some embodiments, the urethane component is Stepanpol PDC-279®. In some embodiments, the urethane component is poly caprolactone triol.

[0033] In an aspect, the reactive species separate from the catechol containing polymer or oligomer is an epoxy resin. In some embodiments, the epoxy resin is an epoxy monomer, an epoxy oligomer, a polyepoxide or combinations thereof; and wherein the epoxy is linear or branched. In some embodiments, the epoxy resin is an epoxy monomer. In some embodiments, the epoxy resin is an epoxy oligomer. In some embodiments, the epoxy resin is a polyepoxide.

[0034] In some embodiments, the epoxy resin is bisphenol A diglycidyl ether, Bisphenol A epoxy resin, bis(4-glycidyloxyphenyl)methane, bisphenol E diglycidyl ether (DGEBE), 2,2'- [l,l-Ethanediylbis(4,l-phenyleneoxymethylene)]di oxirane, bisphenol F diglycidyl ether (DGEBF), poly (bisphenol A-co-epichlorohydrin) or combinations thereof.

[0035] In some embodiments, the epoxy resin is bisphenol A diglycidyl. In some embodiments, the epoxy resin is bisphenol A epoxy resin. In some embodiments, the epoxy is bis(4-glycidyloxyphenyl)methane. In some embodiments, the epoxy resin is bisphenol E diglycidyl ether (DGEBE). In some embodiments, the epoxy resin is 2,2'-[l,l-ethanediylbis (4, l-phenyleneoxymethylene)]di oxirane. In some embodiments, the epoxy resin is bisphenol F diglycidyl ether (DGEBF). In some embodiments, the epoxy resin is poly (bisphenol A-co- epichlorohydrin).

[0036] In an aspect, the reactive species separate from the catechol containing polymer or oligomer is an acrylate monomer or oligomer. In some embodiments, the acrylate monomer or oligomer is an acrylate monomer comprising a vinyl group and at least one of a carboxylic acid ester and a carboxylic acid nitrile; and wherein the acrylate is linear or branched.

[0037] In some embodiments, the acrylate monomer or oligomer is ethyl acrylate, ethylenemethyl acrylate, methyl methacrylate, 2-chloroethyl vinyl ether, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, butyl acrylate, trimethylolpropane triacrylate (TMPTA) or combinations thereof.

[0038] In some embodiments, the acrylate monomer or oligomer is ethyl acrylate. In some embodiments, the acrylate monomer or oligomer is ethylene-methyl acrylate. In someembodiments, the acrylate monomer or oligomer is methyl methacrylate. In some embodiments, the acrylate monomer or oligomer is 2-chloroethyl vinyl ether. In some embodiments, the acrylate monomer or oligomer is 2-hydroxyethyl acrylate. In some embodiments, the acrylate monomer or oligomer is hydroxyethyl methacrylate. In some embodiments, the acrylate monomer or oligomer is butyl acrylate. In some embodiments, the acrylate monomer or oligomer is trimethylolpropane triacrylate (TMPTA).

[0039] In some embodiments, the reactive species separate from the catechol containing polymer or oligomer is a silane. In some embodiments, the reactive species separate from the catechol containing polymer or oligomer is a methacrylate monomer or oligomer. In some embodiments, the reactive species separate from the catechol containing polymer or oligomer is a methacrylate monomer. In some embodiments, the reactive species separate from the catechol containing polymer or oligomer is a methacrylate oligomer.

[0040] In an aspect, the polymeric layer comprises the catalyst, co-catalyst or accelerator; and the catalyst, co-catalyst or accelerator is a urethane catalyst that promotes a urethane polymerization reaction, an epoxy catalyst that promotes an epoxy polymerization reaction, an acrylate catalyst that promotes an acrylate polymerization reaction, or combinations thereof.

[0041] In some embodiments, the catalyst, co-catalyst or accelerator is a urethane catalyst that promotes a urethane polymerization reaction. In some embodiments, the urethane catalyst is an aliphatic amine catalyst, an alicyclic amine catalyst, an alcohol amine catalyst, an aromatic amine catalyst, or an ether amine catalyst.

[0042] In some embodiments, the urethane catalyst is an aliphatic amine catalyst. In some embodiments, the aliphatic amine catalyst is N,N-dimethylcyclohexane, triethylenediamine, N,N,N,N-tetramethylalkylenediamine, N,N,N,N-pentamethyldi ethylenetriamine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylhexadecylamine, N,N- dimethylbutylamine, or combinations thereof.

[0043] In some embodiments, the urethane catalyst is an alicyclic amine catalyst. In some embodiments, the alicyclic amine catalyst is triethylenediamine, N-ethylmorpholine, N- methylmorpholine, N.N-diethylpiperazine, N,N-bis-(a-hydroxypropyl)-2 -methylpiperazine, N-hydroxypropyldimethylmorpholine, or combinations thereof.

[0044] In some embodiments, the urethane catalyst is an alcohol amine catalyst. In some embodiments, the alcohol amine catalyst is triethanolamine or N,N-dem ethylethanolamine.

[0045] In some embodiments, the urethane catalyst is an aromatic amine catalyst. In some embodiments, the aromatic amine catalyst is pyridine or N,N-dimethylpyridine.

[0046] In some embodiments, the urethane catalyst is an ether amine catalyst. In some embodiments, the ether amine catalyst is BDMAEE.

[0047] In some embodiments, the urethane catalyst is l,4-diazabicyclo[2.2.2]octane, K- KAT 6212, benzyldimethylamine or combinations thereof. In some embodiments, the urethane catalyst is l,4-diazabicyclo[2.2.2]octane. In some embodiments, the urethane catalyst is K-KAT 6212. In some embodiments, the urethane catalyst is benzyldimethylamine.

[0048] In some embodiments, the catalyst, co-catalyst or accelerator is an epoxy catalyst that promotes epoxy polymerization.

[0049] Suitable catalysts, co-catalysts or accelerators are substances which accelerate the reaction between amino groups and epoxy groups, such as acids or compounds hydrolyzable to acids. Without limitation, the suitable catalysts, co-catalysts or accelerators are organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2 -nitrobenzoic acid, lactic acid; organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4- dodecylbenzenesulfonic acid; sulfonic esters; other organic or inorganic acids such as phosphoric acid, or mixtures of the aforementioned acids and acid esters; nitrates such as calcium nitrate in particular; or tertiary amines such as 1,4 diazabicyclo[2.2.2]octane, benzyldimethylamine, a-methyl benzyldimethylamine, triethanolamine, dimethylaminopropylamine.

[0050] In some embodiments, the epoxy catalyst is acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, methanesulfonic acid, p-toluenesulfonic acid, 4-dodecyl- benzenesulfonic acid, sulfonic esters, phosphoric acid, calcium nitrate, 1,4- diazabicyclo- [2.2.2] octane, benzyldimethylamine, a-methyl benzyldimethylamine, triethanolamine, dimethylaminopropylamine, N,N-dimethylpiperidine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30), benzyldimethyl-amine (BDMA), 2-(dimethyl- aminomethyl)phenol (DMP-10), N,N dimethylbenzylamine, (dimethylaminomethyl)phenol or combinations thereof.

[0051] In some embodiments, the epoxy catalyst is l,4-diazabicyclo[2.2.2]octane.

[0052] In some embodiments, the catalyst, co-catalyst or accelerator is an acrylate catalyst that promotes acrylate polymerization. In some embodiments, the acrylate catalyst is an acrylic or a free-radical polymerization promoter.

[0053] In some embodiments, the acrylate catalyst is methyl 4-N,N-dimethylamino- phenylacetate (MDMAPA), N,N-dimethylaminoglutethimide (OMAG), N,N-dimethyl-p- toluidine (OMPT), N,N-di-2-Hydroxyethyl-p-toluidine(DHEPT), N,N-di-2-hydroxypropyl-p-toluidine (DHPPT), N,N-dimethyl-sym-xylidine (DMSX), N,N-Bis(3-p-tolyloxy-2-hydroxy- propyl)-m-xylidine (BTX) or combinations thereof.

[0054] In an aspect, the polymeric layer 20 has a thickness of from about 10 nanometers to about 100 microns. In some embodiments, the polymeric layer 20 has a thickness of from about 15 nanometers to about 50 microns. In some embodiments, the polymeric layer 20 has a thickness of from about 15 nanometers to about 15 microns. In some embodiments, the polymeric layer 20 has a thickness of from about 150 nanometers to less than about 15 microns. In some embodiments, the polymeric layer 20 has a thickness of from about 150 nanometers to about 1.5 microns.

[0055] In some embodiments, the polymeric layer 20 has a thickness of from about 10 nanometers to about 100 microns; or from about 10 nanometers to about 100 nanometers; or from about 100 nanometers to about 150 nanometers; or from about 150 nanometers to about 200 nanometers; or from about 200 nanometers to about 250 nanometers; or from about 250 nanometers to about 300 nanometers; or from about 300 nanometers to about 350 nanometers; or from about 350 nanometers to about 400 nanometers; or from about 400 nanometers to about 450 nanometers; or from about 450 nanometers to about 500 nanometers; or from about 500 nanometers to about 550 nanometers; or from about 550 nanometers to about 600 nanometers; or from about 600 nanometers to about 650 nanometers; or from about 650 nanometers to about 700 nanometers; or from about 700 nanometers to about 750 nanometers; or from about 750 nanometers to about 800 nanometers; or from about 800 nanometers to about 850 nanometers; or from about 850 nanometers to about 900 nanometers; or from about 900 nanometers to about 950 nanometers; or from about 950 nanometers to about 1000 nanometers.

[0056] In some embodiments, the polymeric layer 20 has a thickness of from about 1 micron to about 1.5 microns; or from about 1.5 microns to about 5 microns; or from about 5 microns to about 10 microns; or from about 10 microns to about 15 microns; or from about 15 microns to about 20 microns; or from about 20 microns to about 25 microns; or from about 25 microns to about 30 microns; or from about 30 microns to about 35 microns; or from about 35 microns to about 40 microns; or from about 40 microns to about 45 microns; or from about 45 microns to about 50 microns; or from about 50 microns to about 55 microns; or from about 55 microns to about 60 microns; or from about 60 microns to about 65 microns; or from about 65 microns to about 70 microns; or from about 70 microns to about 75 microns; or from about 75 microns to about 80 microns; or from about 80 micronsto about 85 microns; or from about 85 microns to about 90 microns; or from about 90 microns to about 95 microns; or from about 95 microns to about 100 microns.

[0057] In an aspect, the catechol containing polymer or oligomer in the polymeric layer 20 comprises poly-catechol styrene (PCS).

[0058] In some embodiments, the PCS comprises from about 15% catechol to about 50% catechol. In some embodiments, the PCS comprises from about 20% catechol to about 40% catechol. In some embodiments, the PCS comprises from about 25% catechol to about 35% catechol. In some embodiments, the PCS comprises about 25% catechol. In some embodiments, the PCS comprises about 35% catechol.

[0059] In some embodiments, the PCS comprises from about 20% catechol to about 22% catechol; or from about 22% catechol to about 24% catechol; or from about 24% catechol to about 26% catechol; or from about 26% catechol to about 28% catechol; or from about 28% catechol to about 30% catechol; or from about 30% catechol to about 32% catechol; or from about 32% catechol to about 34% catechol; or from about 34% catechol to about 36% catechol; or from about 36% catechol to about 38% catechol; or from about 38% catechol to about 40% catechol.

[0060] In some embodiments, the PCS comprises from about 5% catechol to about 10% catechol. In some embodiments, the PCS comprises from about 10% catechol to about 30% catechol. In some embodiments, the PCS comprises from about 30% catechol to about 50% catechol. In some embodiments, the PCS comprises from about 50% catechol to about 70% catechol. In some embodiments, the PCS comprises from about 70% catechol to about 95% catechol.

[0061] In some embodiments, the polymeric layer further comprises a bulk adhesive layer disposed adjacent to or in contact with the polymeric layer. The bulk adhesive can include a urethane catalyst. In some embodiments, the ratio of bulk adhesive to PCS is about 95:5. In some embodiments, the ratio of bulk adhesive to PCS is about 97.5:2.5. In some embodiments, the ratio of bulk adhesive to PCS is about 99: 1.

[0062] In some embodiments, the polymeric layer further comprises one or more additional polymers including for example, additional poly-catechol-styrene (PCS). In some embodiments, the ratio of polymeric layer to additional PCS is about 90: 10. In some embodiments, the ratio of polymeric layer to additional PCS is about 95:5. In some embodiments, the ratio of polymeric layer to additional PCS is about 97.5:2.5. In some embodiments, the ratio of polymeric layer to additional PCS is about 99: 1.

[0063] In an aspect, the polymeric layer 20 is a continuous layer. In an aspect, the polymeric layer 20 is a non-continuous layer. In an aspect, the polymeric layer 20 is a patterned layer or a textured layer.

[0064] In an aspect, the disclosure is directed to the polymeric layer 20 described herein disposed on a surface of the substrate 10. In some embodiments, the substrate 10 comprises a plastic, a metal, a mineral, a composite, a glass, a silane, concrete, a ceramic, wood, reconstituted wood, fiberglass, asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials. In some embodiments, the substrate 10 comprises a plastic. In some embodiments, the substrate 10 comprises a mineral. In some embodiments, the substrate 10 comprises a ceramic. In some embodiments, the substrate 10 comprises a glass. In some embodiments, the substrate 10 comprises a silane. In some embodiments, the substrate 10 comprises concrete. In some embodiments, the substrate 10 comprises a composite. In some embodiments, the substrate 10 comprises a ceramic. In some embodiments, the substrate 10 comprises wood. In some embodiments, the substrate 10 comprises reconstituted wood. In some embodiments, the substrate 10 comprises asphalt. In some embodiments, the substrate 10 comprises pitch. In some embodiments, the substrate 10 comprises tar. In some embodiments, the substrate 10 comprises bitumen. In some embodiments, the substrate 10 comprises paper. In some embodiments, the substrate 10 comprises fused materials. In some embodiments, the substrate 10 comprises agglomerated materials.

[0065] In some embodiments, the substrate 10 comprises a polymeric compound. In some embodiments, the substrate 10 comprises calcium carbonate. In some embodiments, the substrate 10 comprises a ceramic. In some embodiments, the substrate 10 comprises a metal. In some embodiments, the substrate 10 comprises concrete. In some embodiments, the substrate 10 comprises stone. In some embodiments, the substrate 10 comprises reef material. In some embodiments, the substrate 10 is a coral or a coral base. In some embodiments, the substrate 10 is limestone.

[0066] In some embodiments, the substrate 10 has a smooth surface. In some embodiments, the substrate 10 has a rough surface. In some embodiments, the substrate 10 has an even surface. In some embodiments, the substrate 10 has an uneven surface.

[0067] In some embodiments, the substrate 10 is wet. In some embodiments, the substrate 10 is dry. In some embodiments, the substrate 10 is semi-wet. In some embodiments, the substrate 10 is moist.

[0068] In some embodiments, the surface of the substrate 10 may be treated prior to disposal of the polymeric layer. In some embodiments, the surface of the substrate 10 is anodized. In some embodiments, the surface of the substrate 10 is phosphated.

[0069] In some embodiments, the substrate 10 comprises a metal. In some embodiments, the metal is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, W, Zr, Al, Au, Ag, or combinations thereof, or alloys, blends, or oxides of any of these metals.

[0070] In some embodiments, the metal is Ti, an alloy comprising Ti, a blend comprising Ti, or an oxide comprising Ti. In some embodiments, the metal is V, an alloy comprising V, a blend comprising V, or an oxide comprising V. In some embodiments, the metal is Cr, an alloy comprising Cr, a blend comprising Cr, or an oxide comprising Cr. In some embodiments, the metal is Mn, an alloy comprising Mn, a blend comprising Mn, or an oxide comprising Mn. In some embodiments, the metal is Fe, an alloy comprising Fe, a blend comprising Fe, or an oxide comprising Fe. In some embodiments, the metal is Co, an alloy comprising Co, a blend comprising Co, or an oxide comprising Co. In some embodiments, the metal is Ni, an alloy comprising Ni, a blend comprising Ni, or an oxide comprising Ni. In some embodiments, the metal is Cu, an alloy comprising Cu, a blend comprising Cu, or an oxide comprising Cu. In some embodiments, the metal is W, an alloy comprising W, a blend comprising W, or an oxide comprising W. In some embodiments, the metal is Zr, an alloy comprising Zr, a blend comprising Zr, or an oxide comprising Zr. In some embodiments, the metal is Al, an alloy comprising Al, a blend comprising Al, or an oxide comprising Al. In some embodiments, the metal is Au, an alloy comprising Au, a blend comprising Au, or an oxide comprising Au. In some embodiments, the metal is Ag, an alloy comprising Ag, a blend comprising Ag, or an oxide comprising Ag.

[0071] In some embodiments, the substrate 10 comprises a metal comprising aluminum or steel. In some embodiments, the aluminum or steel is dry. In some embodiments, the aluminum or steel is wet. In some embodiments, the aluminum or steel is semi-wet. In some embodiments, the aluminum or steel is moist.

[0072] The embodiments of the present invention have been described in terms of a thin film on a substrate. In one embodiment, the invention relates to coating of the thin film on porous substrates. Stated differently, the thin film can be coated onto the available surfaces of a porous surface, which includes coating on the external surface of such porous structure as well as the pores and tortuous channels within the porous substrate. It is likely that the thin film may only partially coat the internal surfaces available within the pores of the porous substrate. This invention also relates to coating of such porous substrates wherein a viscosity,surface tension, and hydrophobicity changing additive is used to increase the available internal surface of such porous substrate.

[0073] In an aspect, the disclosure is directed to the polymeric layer 20 described herein in contact with a polymer matrix 30. In some embodiments, the polymer matrix 30 is a bulk adhesive, a sealant, a coating, an ink, a pressure-sensitive adhesive (PSA), a composite or a film. In some embodiments, polymeric layer is in contact with a bulk adhesive. In some embodiments, the ratio of bulk adhesive to polymeric layer is about 90: 10. In some embodiments, the ratio of bulk adhesive to polymeric layer is about 95:5. In some embodiments, the ratio of bulk adhesive to polymeric layer is about 97.5:2.5.

[0074] In some embodiments, the polymer matrix 30 is a bulk adhesive. In some embodiments, the polymer matrix 30 is a sealant. In some embodiments, the polymer matrix 30 is a coating. In some embodiments, the polymer matrix 30 is an ink. In some embodiments, the polymer matrix 30 is a pressure-sensitive adhesive (PSA). In some embodiments, the polymer matrix 30 is a composite. In some embodiments, the polymer matrix 30 is a film.

[0075] In some embodiments, the polymer matrix 30 comprises a polyester. In some embodiments, the polymer matrix 30 comprises a urethane. In some embodiments, the polymer matrix 30 comprises a phenol. In some embodiments, the polymer matrix 30 comprises an epoxy, an acrylic or a silane. In some embodiments, the polymer matrix 30 comprises an epoxy. In some embodiments, the polymer matrix 30 comprises an acrylic. In some embodiments, the polymer matrix 30 comprises a silane. In some embodiments, the polymer matrix 30 comprises a silicone.

[0076] In some embodiments, the polymer matrix 30 is a continuous layer. In some embodiments, the polymer matrix 30 is a non-continuous layer. In some embodiments, the polymer matrix 30 is a patterned layer or a textured layer.

[0077] In some embodiments, the polymeric layer 20 and the polymer matrix 30 form an interpenetrating polymer network (IPN). An IPN as used herein is taken to mean at least two polymer networks that are at least partially interlaced on a molecular scale but not covalently bonded to each other and cannot be separated unless chemical bonds are broken.

[0078] In some embodiments, the polymeric layer 20 and the polymer matrix 30 form a semi-interpenetrating polymer network (SIPN). A SIPN as used herein is taken to mean one or more polymer networks and one or more linear or branched polymer(s) characterized by the penetration on a molecular scale of at least one of the networks by at least some of the linear or branched macromolecules.

[0079] In some embodiments, the polymeric layer 20 and the polymer matrix 30 form a sequential interpenetrating polymer network (SelPN). A SelPN as used herein is taken to mean an interpenetrating polymer network prepared by a process in which the second component network is formed following the formation of the first component network.

[0080] In some embodiments, the polymeric layer 20 and the polymer matrix 30 form a sequential semi-interpenetrating polymer network (SSelPN). A SSelPN as used herein is taken to mean a polymer network prepared by a process in which the linear or branched components are formed following the completion of the reactions that lead to the formation of the network(s) or vice versa.

[0081] In an aspect, the bulk adhesive layer 30 comprises urethane or a urethane component or a catechol containing oligomer or polymer. In some embodiments, the urethane or a urethane component comprises methylene diphenyl diisocyanate (MDI) resins. In some embodiments, the bulk adhesive layer 30 comprises methylene diphenyl diisocyanate (MDI) resins. In some embodiments, the bulk adhesive layer 30 comprises catechol containing oligomer or polymer. In some embodiments, the catechol containing oligomer or polymer comprises poly catechol styrene (PCS).

[0082] In some embodiments, the bulk adhesive layer 30 further comprises calcium carbonate, silica, NEVEX® resin, or combinations thereof. In some embodiments, the bulk adhesive layer 30 further comprises calcium carbonate. In some embodiments, the bulk adhesive layer 30 further comprises silica. In some embodiments, the bulk adhesive layer 30 further comprises NEVEX® resin.

[0083] In an aspect, the bulk adhesive layer 30 is a moisture curing adhesive.

[0084] In an aspect, the disclosure is directed to the polymeric layer 20 described herein disposed on a surface of the substrate 5. In some embodiments, the substrate 5 comprises a polymeric compound, calcium carbonate, a ceramic, a metal, concrete, stone, reef material or combinations thereof; and wherein the substrate is wet, dry, semi-wet or moist.

[0085] In some embodiments, a second substrate 50 is disposed on the polymer matrix 30. In some embodiments, the second substrate 50 is disposed on and in contact with the polymer matrix 30. In some embodiments, a second polymeric layer 20 is disposed between the polymer matrix 30 and the second substrate 50.

[0086] In an aspect, the disclosure is directed to methods of making a substrate comprising disposing the polymeric layer 20 described herein on a surface of the substrate 10. The methods of disposing the polymeric layer 20 described herein are not particularly limited and will be recognized by those skilled in the art.

[0087] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 by spin coating, dip coating, spray coating, inkjet printing, flood coating, brushing, wiping, or the like. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 by spin coating. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 by dip coating. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 by spray coating. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 by inkjet printing. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 by flood coating. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 by brushing. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 by wiping.

[0088] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10, wherein the polymeric layer 20 is applied to the substrate 10 as a solution. In some embodiments, the solution comprises from about 0.001% by weight to about 10% by weight of the catechol containing polymer or oligomer. In some embodiments, the solution comprises from about 0.01% by weight to about 5% by weight of the catechol containing polymer or oligomer. In some embodiments, the solution comprises from about 0.01% by weight to about 1% by weight of the catechol containing polymer or oligomer. In some embodiments, the solution comprises from about 0.1% by weight to about 1% by weight of the catechol containing polymer or oligomer.

[0089] In some embodiments, the solution comprises from about 0.001% by weight to about 0.005% by weight of the catechol containing polymer or oligomer; or from about 0.005% by weight to about 0.01% by weight of the catechol containing polymer or oligomer; or from about 0.01% by weight to about 0.02% by weight of the catechol containing polymer or oligomer; or from about 0.02% by weight to about 0.03% by weight of the catechol containing polymer or oligomer; or from about 0.03% by weight to about 0.04% by weight of the catechol containing polymer or oligomer; or from about 0.04% by weight to about 0.05% by weight of the catechol containing polymer or oligomer; or from about 0.05% by weight to about 0.06% by weight of the catechol containing polymer or oligomer; or from about 0.06% by weight to about 0.07% by weight of the catechol containing polymer or oligomer; or from about 0.07% by weight to about 0.08% by weight of the catechol containing polymer or oligomer; or from about 0.08% by weight to about 0.09% by weight of the catechol containing polymer or oligomer; or from about 0.09% by weight to about 0.1% by weight ofthe catechol containing polymer or oligomer; or from about 0.1% by weight to about 0.11% by weight of the catechol containing polymer or oligomer; or from about 0.11% by weight to about 0.12% by weight of the catechol containing polymer or oligomer; or from about 0.12% by weight to about 0.13% by weight of the catechol containing polymer or oligomer; or from about 0.13% by weight to about 0.14% by weight of the catechol containing polymer or oligomer; or from about 0.14% by weight to about 0.15% by weight of the catechol containing polymer or oligomer; or from about 0.15% by weight to about 0.2% by weight of the catechol containing polymer or oligomer; or from about 0.2% by weight to about 0.25% by weight of the catechol containing polymer or oligomer; or from about 0.25% by weight to about 0.3% by weight of the catechol containing polymer or oligomer; or from about 0.3% by weight to about 0.35% by weight of the catechol containing polymer or oligomer; or from about 0.35% by weight to about 0.4% by weight of the catechol containing polymer or oligomer; or from about 0.4% by weight to about 0.45% by weight of the catechol containing polymer or oligomer; or from about 0.45% by weight to about 0.5% by weight of the catechol containing polymer or oligomer; or from about 0.5% by weight to about 0.75% by weight of the catechol containing polymer or oligomer; or from about 0.75% by weight to about 1% by weight of the catechol containing polymer or oligomer; or from about 1.25% by weight to about 1.5% by weight of the catechol containing polymer or oligomer; or from about 1.5% by weight to about 1.75% by weight of the catechol containing polymer or oligomer; or from about 1.75% by weight to about 2% by weight of the catechol containing polymer or oligomer.

[0090] In some embodiments, the catechol containing polymer or oligomer used in the solution is poly-catechol styrene (PCS). In some embodiments, the solution comprises from about 0.001% by weight to about 10% by weight of PCS. In some embodiments, the solution comprises from about 0.01% by weight to about 5% by weight of PCS. In some embodiments, the solution comprises from about 0.01% by weight to about 1% by weight of PCS. In some embodiments, the solution comprises from about 0.1% by weight to about 1% by weight of PCS.

[0091] In some embodiments, the solution comprises from about 0.001% by weight to about 0.005% by weight of PCS; or from about 0.005% by weight to about 0.01% by weight of PCS; or from about 0.01% by weight to about 0.02% by weight of PCS; or from about 0.02% by weight to about 0.03% by weight of PCS; or from about 0.03% by weight to about 0.04% by weight of PCS; or from about 0.04% by weight to about 0.05% by weight of PCS; or from about 0.05% by weight to about 0.06% by weight of PCS; or from about 0.06% byweight to about 0.07% by weight of PCS; or from about 0.07% by weight to about 0.08% by weight of PCS; or from about 0.08% by weight to about 0.09% by weight of PCS; or from about 0.09% by weight to about 0.1% by weight of PCS; or from about 0.1% by weight to about 0.11% by weight of PCS; or from about 0.11% by weight to about 0.12% by weight of PCS; or from about 0.12% by weight to about 0.13% by weight of PCS; or from about 0.13% by weight to about 0.14% by weight of PCS; or from about 0.14% by weight to about 0.15% by weight of PCS; or from about 0.15% by weight to about 0.2% by weight of PCS; or from about 0.2% by weight to about 0.25% by weight of PCS; or from about 0.25% by weight to about 0.3% by weight of PCS; or from about 0.3% by weight to about 0.35% by weight of PCS; or from about 0.35% by weight to about 0.4% by weight of PCS; or from about 0.4% by weight to about 0.45% by weight of PCS; or from about 0.45% by weight to about 0.5% by weight of PCS; or from about 0.5% by weight to about 0.75% by weight of PCS; or from about 0.75% by weight to about 1% by weight of PCS; or from about 1.25% by weight to about 1.5% by weight of PCS; or from about 1.5% by weight to about 1.75% by weight of PCS; or from about 1.75% by weight to about 2% by weight of PCS.

[0092] In some embodiments, the solution comprises PCS having a molecular with of from about 5,000 to about 10,000. In some embodiments, the solution comprises PCS having a molecular of from about 10,000 to about 15,000. In some embodiments, the solution comprises PCS having a molecular of from about 15,000 to about 20,000. In some embodiments, the solution comprises PCS having a molecular of from about 20,000 to about 25,000. In some embodiments, the solution comprises PCS having a molecular of from about 25,000 to about 30,000. In some embodiments, the solution comprises PCS having a molecular of from about 30,000 to about 35,000. In some embodiments, the solution comprises PCS having a molecular of from about 35,000 to about 40,000. In some embodiments, the solution comprises PCS having a molecular of from about 40,000 to about 45,000. In some embodiments, the solution comprises PCS having a molecular of from about 45,000 to about 50,000. In some embodiments, the solution comprises PCS having a molecular of from about 50,000 to about 55,000. In some embodiments, the solution comprises PCS having a molecular of from about 55,000 to about 60,000. In some embodiments, the solution comprises PCS having a molecular of from about 60,000 to about 65,000. In some embodiments, the solution comprises PCS having a molecular of from about 65,000 to about 70,000. In some embodiments, the solution comprises PCS having a molecular of from about 70,000 to about 75,000. In some embodiments, the solution comprises PCS having a molecular of from about 75,000 to about 80,000. In someembodiments, the solution comprises PCS having a molecular of from about 80,000 to about 85,000. In some embodiments, the solution comprises PCS having a molecular of from about 85,000 to about 90,000. In some embodiments, the solution comprises PCS having a molecular of from about 90,000 to about 95,000. In some embodiments, the solution comprises PCS having a molecular of from about 95,000 to about 100,000. In some embodiments, the solution comprises PCS having a molecular of from about 5,000 to about 100,000 including any and all increments therebetween. In some embodiments, the solution comprises PCS having a molecular of about 40,000. In some embodiments, the solution comprises PCS having a molecular of about 80,000.

[0093] In some embodiments, the solution also comprises an aqueous or organic solvent for dissolving the catechol containing polymer or oligomer. In some embodiments, the organic solvent is acetone, toluene, chloroform, dichloromethane (DCM), ethyl acetate, methyl ethyl ketone (MEK) or a combination thereof.

[0094] In some embodiments, the organic solvent is acetone. In some embodiments, the organic solvent is toluene. In some embodiments, the organic solvent is chloroform. In some embodiments, the organic solvent is dichloromethane (DCM). In some embodiments, the organic solvent is ethyl acetate. In some embodiments, the organic solvent is methyl ethyl ketone (MEK). In some embodiments, the organic solvent is a combination of acetone and toluene. In some embodiments, the organic solvent is acetone and the catechol containing polymer or oligomer is PCS. In some embodiments, the organic solvent is toluene and the catechol containing polymer or oligomer is PCS. In some embodiments, the organic solvent is a combination of acetone and toluene and the catechol containing polymer or oligomer is PCS.

[0095] The pH of the solution is not particularly limited. In some embodiments, the pH of the solution is about 3; or about 3.5; or about 4; or about 4.5; or about 5; or about 5.5; or about 6; or about 6.5; or about 7; or about 7.5; or about 8; or about 8.5; or about 9; or about 9.5; or about 10; or about 10.5; or about 11.

[0096] In some embodiments, the pH of the solution is from about 3 - 3.5; or about 3.5 - 4; or about 4 - 4.5; or about 4.5 - 5; or about 5 - 5.5; or about 5.5 - 6; or about 6 - 6.5; or about 6.5 - 7; or about 7 - 7.5; or about 7.5 - 8; or about 8 - 8.5; or about 8.5 - 9; or about 9 - 9.5; or about 9.5 - 10; or about 10 - 10.5; or about 10.5 - 11.

[0097] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10, wherein the substrate 10 comprises a plastic, a metal, a mineral, a composite, a glass, a silane, concrete, a ceramic, wood, reconstituted wood,asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials; and wherein the substrate is wet, dry, semi-wet or moist.

[0098] In some embodiments, the methods of making a substrate 10 comprise disposing the polymeric layer 20 on a substrate 10 comprising plastic. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising metal. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising a mineral. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising a composite. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising glass. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising silane. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising concrete. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising ceramic. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising wood. In some embodiments, the methods comprise disposing polymeric layer 20 on a substrate 10 comprising reconstituted wood. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising asphalt. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising pitch. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising tar. In some embodiments, the methods comprise disposing the polymeric layer on a substrate comprising bitumen. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising paper. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising fused materials. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising agglomerated materials.

[0099] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a wet substrate 10. In some embodiments, the methods comprise disposing the polymeric layer 20 on a dry substrate 10. In some embodiments, the methods comprise disposing the polymeric layer 20 on a semi-wet substrate 10. In some embodiments, the methods comprise disposing the polymeric layer 20 on a moist substrate 10

[0100] In some embodiments, the methods of making a substrate comprise treating a surface of the substrate 10 prior to disposal of the polymeric layer described herein. In some embodiments, the methods comprise anodizing a surface of the substrate 10 prior to disposalof the polymeric layer. In some embodiments, the methods comprise phosphating a surface of the substrate 10 prior to disposal of the polymeric layer.

[0101] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 comprising metal. In some embodiments, the metal is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, W, Zr, Al, or combinations thereof, or alloys, blends, or oxides of any of these metals.

[0102] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 comprising Ti, an alloy comprising Ti, a blend comprising Ti, or an oxide comprising Ti. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising V, an alloy comprising V, a blend comprising V, or an oxide comprising V. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising Cr, an alloy comprising Cr, a blend comprising Cr, or an oxide comprising Cr. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising Mn, an alloy comprising Mn, a blend comprising Mn, or an oxide comprising Mn. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising Fe, an alloy comprising Fe, a blend comprising Fe, or an oxide comprising Fe. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising Co, an alloy comprising Co, a blend comprising Co, or an oxide comprising Co. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising Ni, an alloy comprising Ni, a blend comprising Ni, or an oxide comprising Ni. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising Cu, an alloy comprising Cu, a blend comprising Cu, or an oxide comprising Cu. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising W, an alloy comprising W, a blend comprising W, or an oxide comprising W. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising Zr, an alloy comprising Zr, a blend comprising Zr, or an oxide comprising Zr. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising Al, an alloy comprising Al, a blend comprising Al, or an oxide comprising Al.

[0103] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 comprising aluminum or steel. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising dry aluminum or dry steel. In some embodiments, the methods comprise disposing the polymericlayer 20 on a substrate 10 comprising semi-wet aluminum or semi-wet steel. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 comprising moist aluminum or moist steel.

[0104] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 comprising anodized aluminum. In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 comprising phosphated steel.

[0105] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 in a dry environment. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 in an ambient environment. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 in a humid environment. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 in an aqueous environment. In some embodiments, the methods comprise disposing the polymeric layer 20 on a substrate 10 in an underwater environment.

[0106] In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 as a continuous layer. In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 as a non-continuous layer. In some embodiments, the methods of making a substrate comprise disposing the polymeric layer 20 on a substrate 10 as a patterned layer or a textured layer.

[0107] In an aspect, the disclosure is directed to methods of making a substrate comprising disposing the polymeric layer 20 described herein on a surface of the substrate 10, and further comprising disposing a polymer matrix 30 on the polymeric layer 20. The methods of disposing the polymer matrix 30 described herein are not particularly limited and will be recognized by those skilled in the art.

[0108] In some embodiments, the methods of making a substrate comprise disposing the polymer matrix 30 on the polymeric layer 20 by spin coating, dip coating, spray coating, ink jet printing, flood coating, brushing, wiping, or the like. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 by spin coating. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 by dip coating. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 by spray coating. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 by inkjet printing. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymericlayer 20 by flood coating. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 by brushing. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 by wiping.

[0109] In some embodiments, the polymer matrix 30 is a bulk adhesive, a sealant, a coating, an ink, a pressure-sensitive adhesive (PSA), a composite or a film.

[0110] In some embodiments, the methods of making a substrate comprise disposing a bulk adhesive 30 on the polymeric layer 20. In some embodiments, the methods comprise disposing a sealant 30 on the polymeric layer 20. In some embodiments, the methods comprise disposing a coating 30 on the polymeric layer 20. In some embodiments, the methods comprise disposing an ink 30 on the polymeric layer 20. In some embodiments, the methods comprise disposing a pressure-sensitive adhesive (PSA) 30 on the polymeric layer 20. In some embodiments, the methods comprise disposing a composite 30 on the polymeric layer 20. In some embodiments, the methods comprise disposing a film 30 on the polymeric layer 20.

[0111] In some embodiments, the polymer matrix 30 comprises a polyester, a urethane, a phenol, an epoxy, an acrylic, a silane or a silicone.

[0112] In some embodiments, the methods of making a substrate comprise disposing a polyester on the polymeric layer 20. In some embodiments, the methods comprise disposing a urethane on the polymeric layer 20. In some embodiments, the methods comprise disposing a phenol on the polymeric layer 20. In some embodiments, the methods comprise disposing an epoxy, an acrylic or a silane on the polymeric layer 20. In some embodiments, the methods comprise disposing an epoxy on the polymeric layer 20. In some embodiments, the methods comprise disposing an acrylic on the polymeric layer 20. In some embodiments, the methods comprise disposing a silane on the polymeric layer 20. In some embodiments, the methods comprise disposing a silicone on the polymeric layer 20.

[0113] In some embodiments, the methods of making a substrate comprise disposing the polymer matrix 30 on the polymeric layer 20 in a dry environment. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 in an ambient environment. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer in a humid environment. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 in an aqueous environment. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 in an underwater environment.

[0114] In some embodiments, the methods of making a substrate comprise disposing the polymer matrix 30 on the polymeric layer 20 on a substrate as a continuous layer. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 as a non-continuous layer. In some embodiments, the methods comprise disposing the polymer matrix 30 on the polymeric layer 20 as a patterned layer or a textured layer.

[0115] In some embodiments, the methods for disposing the polymer matrix 30 as a non- continuous layer or for disposing the polymeric layer 20 as a non-continuous layer comprise disposing the layers in an ordered pattern or a stochastic pattern.

[0116] In some embodiments, the ordered pattern comprises strips, a grid, concentric circles or a dot pattern. In some embodiments, the methods comprise disposing the polymer matrix 30 and / or the polymeric layer 20 as strips. In some embodiments, the methods comprise disposing the polymer matrix 30 and / or the polymeric layer 20 as a grid. In some embodiments, the methods comprise disposing the polymer matrix 30 and / or the polymeric layer 20 as concentric circles. In some embodiments, the methods comprise disposing the polymer matrix 30 and / or the polymeric layer 20 as a dot pattern.

[0117] In some embodiments, the methods comprise disposing the polymer matrix 30 and / or the polymeric layer 20 stochastically.

[0118] The polymer matrix 30 and / or the polymeric layer 20 can be disposed in particular shapes or in an amorphous manner. In some embodiments, the methods comprise disposing the polymer matrix 30 and / or the polymeric layer 20 as a dot, a circle, a square, a rectangle, a pentagon, a hexagon; or as amorphous.

[0119] In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as a dot. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as a circle. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as an oval. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as a triangle. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as a square. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as a rectangle. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as a pentagon. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as a hexagon. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are amorphous.

[0120] In some embodiments, the methods comprise disposing the polymer matrix 30 and / or the polymeric layer 20 as gridlines, crisscross lines, random lines, concentric circles, eccentric circles, spaghetti patterns and flat strips.

[0121] In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as gridlines. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as crisscross lines. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as random lines. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as concentric circles. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as eccentric circles. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as a spaghetti pattern. In an embodiment, the polymer matrix 30 and / or the polymeric layer 20 are shaped as a flat strip.

[0122] In an aspect, the disclosure is directed to a layered structure comprising the polymeric layer 20 described herein.

[0123] In an aspect, the disclosure is directed to a layered structure comprising the polymeric layer 20 described herein disposed on a substrate 10.

[0124] In an aspect, the disclosure is directed to a layered structure comprising the polymeric layer 20 described herein disposed between a substrate 10 and a polymer matrix 30.

[0125] In an aspect, the disclosure is directed to a layered structure comprising the polymeric layer 20 described herein disposed between a substrate 10 and a polymer matrix 30, and further comprising a second substrate 50 disposed on the polymer matrix 30.

[0126] In an aspect, the disclosure is directed to a layered structure comprising the polymeric layer 20 described herein disposed between a substrate 10 and a polymer matrix 30, and further comprising a second polymeric layer 20 disposed on the polymer matrix 30.

[0127] In an aspect, the disclosure is directed to a layered structure comprising the polymeric layer 20 described herein disposed between a substrate 10 and a polymer matrix 30, and further comprising a second polymeric layer 20 disposed between the second substrate 50 and the polymer matrix 30.

[0128] In an aspect, the disclosure is directed to an article comprising the polymeric layer 20 described herein.

[0129] In an aspect, the disclosure is directed to an article comprising the polymeric layer 20 described herein disposed on a substrate 10.

[0130] In an aspect, the disclosure is directed to an article comprising the polymeric layer 20 described herein disposed between a substrate 10 and a polymer matrix 30.

[0131] In an aspect, the disclosure is directed to an article comprising the polymeric layer 20 described herein disposed between a substrate 10 and a polymer matrix 30, and further comprising a second substrate 50 disposed on the polymer matrix 30.

[0132] In an aspect, the disclosure is directed to an article comprising the polymeric layer 20 described herein disposed between a substrate 10 and a polymer matrix 30, and further comprising a second polymeric layer 20 disposed on the polymer matrix 30.

[0133] In an aspect, the disclosure is directed to an article comprising the polymeric layer 20 described herein disposed between a substrate 10 and a polymer matrix 30, and further comprising a second polymeric layer 20 disposed between the second substrate 50 and the polymer matrix 30.

[0134] EXAMPLES

[0135] The following Examples is provided to illustrate some of the concepts described within this disclosure. While the Examples are considered to provide an embodiment, it should not be considered to limit the more general embodiments described herein.

[0136] Example 1 - Adhesive / PCS hybrid composition

[0137] In some aspects, the present invention provide a composition that includes a single poly(catechol-co-styrene) (PCS) additive that functions as a catalyst, cross-linker, and adhesion promoter.

[0138] The composition of the present disclosure has its strength, handling, and settling time tuned by the molecular weight of the poly (catechol -co-styrene) additive, the concentration PCS is added in, and the solvent that is used.

[0139] It is additionally important to note that the SEATAK™ / PCS hybrid gained an increase in underwater tackiness that was not seen in the SEATAK™ formulation without PCS. SEATAK™ is the composition as disclosed in PCT application No PCT / US2021 / 052202, which is incorporated herein in its entirety. This increase in tackiness makes the adhesive easier to apply in underwater conditions.

[0140] SEATAK™ is a moisture-cure polyurethane adhesive system. Formulation of SEATAK™ to incorporate proprietary poly(catechol-co-styrene) (PCS) as a one-part or two- part adhesive system provides a catalyst, cross-linker, and adhesion promoter. Additionally, the PCS has the ability to tune the curing and handling time. Having control over the rate at which the adhesive cures is critical for its viability in different applications - one cure time does not fit all.

[0141] The SEATAK™ / PCS hybrid adhesive system provided the strongest tensile and peel tests at 95:5 SEATAK™:PCS ratio. 5 wt.% PCS is dissolved in methyl ethyl ketone in a 1 : 1 polymer: solvent ratio. This polymer / solvent mixture functions as the Part B of theadhesive system. Part A of the adhesive system is the urethane adhesive, which is added at 95 wt.%. The two parts are added together and mixed until homogenous.

[0142] The cure time of the SEATAK™ adhesive system without the PCS additive can be up to seven days. The cure time of the two-part SEATAK™:PCS adhesive system is exceptionally faster (as quick as 5 minutes) and can be adjusted to an optimum for different applications.

[0143] Without being bound to theory, it is hypothesized that the catechol functional groups act as a cross-linking catalyst between the urethane polymer or possibly the isocyanate monomer and the PCS, the polymer chains of the urethane and PCS entangle which results in a stronger polymer network, the catechol functional group allows for a stronger bond to form between the surface and adhesive, or perhaps a combination of these factors is at play.

[0144] The molecular weight of the PCS in the Part B of this adhesive system influences the curing time. As the molecular weight of the PCS used increases, the curing time decreases. A 90: 10 (SEATAK™:PCS) using a 40,000 molecular weight PCS will have four times the cure time (120 minutes) when compared to a 90: 10 (SEATAK™:PCS) using an 80,000 molecular weight PCS (30 minutes).

[0145] The concentration of PCS used influences the curing time as well. As the concentration of the PCS decreases, the curing time of the adhesive increases. A 90: 10 SEATAK™:PCS has a 30-minute cure time, a 95:5 has a 50-minute cure time, and a 97.5:2.5 has an 80-minute cure time.

[0146] Choice of solvent also influences the handling, settling, and cure time and efficacy of the SEATAK™:PCS hybrid adhesive system. The isocyanate functional groups in the part A of the adhesive system can readily react with alcohols, amines, and other functional groups present in solvent choice. It is hypothesized that the handling, settling, and cure times of the SEATAK™:PCS hybrid system would decrease in solvents with reactive functional groups (e.g., water, methanol, dimethylformamide) and increase in solvents without reactive functional groups (e.g., ethers).

[0147] As previously mentioned, control over handling, settling, and cure times is critical for adopting the SEATAK™:PCS hybrid adhesive system into different applications.

[0148] It is additionally important to note that the SEATAK™:PCS hybrid gained an increase in underwater tackiness that was not seen in the SEATAK™ formulation without PCS. This increase in tackiness makes the adhesive easier to apply in underwater conditions.

[0149] Example 2 - Optimizing timing of use

[0150] Handling time of the SEATAK™ / PCS hybrid was determined by preparing the two-part adhesive system (described below in part B) and measuring the time in which it was still able to be used and manipulated. When the adhesive hardened to the point of not being able to mechanically manipulate it, it was considered to have reached the end of the handling time. Handling time is important because it indicates the amount of time that you have when mixing and using the adhesive.

[0151] Settling time was determined by starting at the end of the handling time and periodically testing the adhesive using a modified ASTM D2377 “Tack Free” measurement.

[0152] Cure strength of the SEATAK™:PCS hybrid adhesive system was measured through peel tests using a VERSATHANE™ substrate. A baseline was established comparing formulations of different concentrations, different molecular weights of the PCS additive being used, and with different solvents.

[0153] Initial cure time tests were performed in order to evaluate handling times. Initial test results including initial calculations for isocyanate and catechol ratios are found in Table 1 below.

[0154] Table 1. Cure Time Test: Test Compound A in MEK / Ethylene Glycol (90 / 10)

[0155] Example 3 - Preparation of PCS -containing wet-bond adhesive

[0156] Weigh out PCS at 5% of total desired weight of adhesive needed. Pipet Methyl Ethyl Ketone (MEK / 2-Butanol) at the same weight of the PCS, this is now Part B. Mix the 2 components and wait for PCS to fully dissolve in the solvent, be sure to cover the container to prevent solvent from flashing off. Mix in part A, urethane adhesive, at 95% of total weight desired, mix until homogeneous, is easier to combine if the PCS / Solvent system is heated up in oven. Samples have been prepared in a two-part adhesive tube with a screw mixing nozzle. A single Part A has been prepared containing SEATAK™ and dry PCS without solvent. Solvent is necessary to initiate the curing process. However, in the case of the single Part A with dry PCS, water activates the curing process and helps solvate the PCS.Retardants can be added to the single Part A system to slow down cure time.

[0157] Example 4 - Concentration of PCS for optimized bond strength

[0158] Ratios of Part A and Part B were the initial look into a two-part adhesive system. Part A urethane adhesive was originally the additive to PCS, but in a different solvent, to promote adhesion but Part A would not dissolve in the solvent and would not become the homogenous mixture we needed. With Part A not dissolving it the ratios were switched to have PCS, in a different solvent, mixed into the urethane adhesive. When mixed, much more homogenous mixtures were observed, and testing was moved forward with the mixtures. The ratios attempted, (%Part A by weight, %Part B by weight), were: (10%, 90%), (20%, 80%), (30%, 70%), (70%, 30%), (80%, 20%), (90%, 10%), (95%, 5%), (97.5%, 2.5%). Lap shear adhesion shear testing was completed on the three working combinations, (70%, 30%), (80%, 20%), (90%, 10%), and it was concluded that the lower the percentage of Part B the stronger the shear strength was.

[0159] Example 5 - Expansion Study

[0160] In order to evaluate cure expansion underwater, an expansion study was performed. Results from the expansion study are found in Table 2 below.

[0161] Table 2. Expansion Study Results

[0162] ASPECTS

[0163] The following Aspects are illustrative only and do not limit the scope of the present disclosure or the appended claims. Any part or parts of any one or more Aspects can be combined with any part or parts of any one or more other Aspects.

[0164] Aspect 1. A polymeric layer comprising a catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of a primary amine or a secondary amine; wherein the polymeric layer optionally comprises a reactive material that is not reactive with catechol or quinone.

[0165] Aspect 2. The polymeric layer of Aspect 1 further comprising a bulk adhesive layer disposed adjacent to and in contact with the polymeric layer.

[0166] Aspect 3. The polymeric layer of Aspect 2, wherein the bulk adhesive layer is a moisture curing adhesive.

[0167] Aspect 4. The polymeric layer of any one of Aspects 1 to 3, wherein the polymeric layer comprises the reactive material and the reactive material is a resin, an oligomer, a polymer or a monomer.

[0168] Aspect 5. The polymeric layer of Aspect 4, wherein the reactive material is a urethane or a urethane component.

[0169] Aspect 6. The polymeric layer of Aspect 1, wherein the polymeric layer has a thickness of from about 10 nanometers to about 100 microns.

[0170] Aspect 7. The polymeric layer of Aspect 1, wherein the polymeric layer has a thickness of from about 15 nanometers to about 50 microns.

[0171] Aspect 8. The polymeric layer of Aspect 1, wherein the polymeric layer has a thickness of from about 15 nanometers to about 15 microns.

[0172] Aspect 9. The polymeric layer of Aspect 1, wherein the polymeric layer has a thickness of from about 150 nanometers to less than about 15 microns.

[0173] Aspect 10. The polymeric layer of Aspect 1, wherein the polymeric layer has a thickness of from about 150 nanometers to about 1.5 microns.

[0174] Aspect 11. The polymeric layer of Aspect 1, wherein the catechol containing polymer or oligomer comprises poly-catechol styrene (PCS).

[0175] Aspect 12. The polymeric layer of Aspect 11, wherein the poly-catechol styrene (PCS) comprises from about 25% catechol to about 35% catechol.

[0176] Aspect 13. The polymeric layer of Aspect 11, wherein the poly-catechol styrene (PCS) comprises from about 5% catechol to about 50% catechol.

[0177] Aspect 14. The polymeric layer of Aspect 2, wherein the bulk adhesive layer comprises methylene diphenyl diisocyanate (MDI) resins or polycatechol styrene (PCS).

[0178] Aspect 15. The polymeric layer of Aspect 11, wherein the poly-catechol styrene (PCS) has a molecular weight of from about 30,000 to about 90,000.

[0179] Aspect 16. A substrate comprising the polymeric layer of Aspect 1 disposed on a surface of the substrate.

[0180] Aspect 17. The substrate of Aspect 16, wherein the substrate comprises a polymeric compound, calcium carbonate, a ceramic, a metal, concrete, stone, reef material, a plastic, a mineral, a composite, a glass, a silane, concrete, wood, reconstituted wood, fiberglass, asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials or combinations thereof; and wherein the substrate is wet, dry, semi-wet or moist.

[0181] Aspect 18. The substrate of Aspect 16, wherein the substrate is wet.

[0182] Aspect 19. The substrate of Aspect 16, wherein the substrate is dry.

[0183] Aspect 20. A second substrate in contact with the substrate of Aspect 16.

[0184] Aspect 21. The second substrate of Aspect 20, wherein the second substrate is disposed on the polymeric layer.

[0185] Aspect 22 The second substrate of Aspect 21, wherein the second substrate comprises a polymeric compound, calcium carbonate, a ceramic, a metal, concrete, stone, reef material, a plastic, a mineral, a composite, a glass, a silane, concrete, wood, reconstituted wood, fiberglass, asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials or combinations thereof; and wherein the second substrate is wet, dry, semi-wet or moist.

[0186] Aspect 23. The second substrate of Aspect 20, wherein the second substrate is wet.

[0187] Aspect 24. The second substrate of Aspect 20, wherein the second substrate is dry.

[0188] Aspect 25. The second substrate of Aspect 20, further comprising a second bulk adhesive layer disposed on the polymeric layer.

[0189] Aspect 26. The second substrate of Aspect 23, wherein the second bulk adhesive layer comprises urethane or a urethane component.

[0190] Aspect 27. A method of making a substrate comprising disposing the polymeric layer of Aspect 1 on a surface of the substrate.

[0191] Aspect 28. The method of Aspect 27, wherein the substrate comprises a polymeric compound, calcium carbonate, a ceramic, a metal, concrete, stone, reef material, a plastic, a mineral, a composite, a glass, a silane, concrete, wood, reconstituted wood, fiberglass, asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials or combinations thereof.

[0192] Aspect 29. The method of Aspect 27, wherein the disposing comprises disposing in a dry environment.

[0193] Aspect 30. The method of Aspect 29, wherein the dry environment is an ambient environment.

[0194] Aspect 31. The method of Aspect 27, wherein the disposing comprises disposing in an aqueous environment.

[0195] Aspect 32 The method of Aspect 31, wherein the aqueous environment is an underwater environment.

[0196] Aspect 33. The method of Aspect 27, further comprising disposing a bulk adhesive layer on the polymeric layer.

[0197] Aspect 34. The method of Aspect 33 wherein the bulk adhesive layer comprises urethane or a urethane component.

[0198] Aspect 35. The method of Aspect 27, further comprising disposing a second substrate on the substrate.

[0199] Aspect 36. The method of Aspect 35, wherein the second substrate is disposed on the polymeric layer.

[0200] Aspect 37. The method of Aspect 35, wherein the second substrate comprises a polymeric calcium carbonate, a ceramic, a metal, concrete, stone, reef material, a plastic, a mineral, a composite, a glass, a silane, concrete, wood, reconstituted wood, fiberglass,asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials or combinations thereof; and wherein the second substrate is wet, dry, semi -wet or moist.

[0201] Aspect 38. The method of Aspect 35, wherein the second substrate is wet.

[0202] Aspect 39. The method of Aspect 35, wherein the second substrate is dry.

[0203] Aspect 40. The method of Aspect 35, further comprising disposing a second bulk adhesive layer between the second substrate and the polymeric layer.

[0204] Aspect 41. The method of Aspect 40, wherein the second bulk adhesive layer comprises urethane or a urethane component.

[0205] Aspect 42. A layered structure comprising the polymeric layer of Aspect 1 disposed between a first substrate and a second substrate.

[0206] Aspect 43. An article comprising the polymeric layer of Aspect 1.

Claims

What is Claimed:

1. A polymeric layer comprising a catechol containing polymer or oligomer, wherein said catechol presents as a catechol and / or as a semi -quinone and / or as a quinone without the presence of a primary amine or a secondary amine; wherein the polymeric layer optionally comprises a reactive material that is not reactive with catechol or quinone.

2. The polymeric layer of claim 1 further comprising a bulk adhesive layer disposed adjacent to and in contact with the polymeric layer.

3. The polymeric layer of claim 2, wherein the bulk adhesive layer is a moisture curing adhesive.

4. The polymeric layer of any one of claims 1 to 3, wherein the polymeric layer comprises the reactive material and the reactive material is a resin, an oligomer, a polymer or a monomer.

5. The polymeric layer of claim 4, wherein the reactive material is a urethane or a urethane component.

6. The polymeric layer of any one of claims 1 to 5, wherein the polymeric layer has a thickness of from about 10 nanometers to about 100 microns.

7. The polymeric layer of any one of claims 1 to 6, wherein the polymeric layer has a thickness of from about 15 nanometers to about 50 microns.

8. The polymeric layer of any one of claims 1 to 7, wherein the polymeric layer has a thickness of from about 15 nanometers to about 15 microns.

9. The polymeric layer of any one of claims 1 to 8, wherein the polymeric layer has a thickness of from about 150 nanometers to less than about 15 microns.

10. The polymeric layer of any one of claims 1 to 9, wherein the polymeric layer has a thickness of from about 150 nanometers to about 1.5 microns.

11. The polymeric layer of claim 1, wherein the catechol containing polymer or oligomer comprises poly-catechol styrene (PCS).

12. The polymeric layer of claim 11, wherein the poly -catechol styrene (PCS) comprises from about 25% catechol to about 35% catechol.

13. The polymeric layer of claim 11, wherein the poly -catechol styrene (PCS) comprises from about 5% catechol to about 50% catechol.

14. The polymeric layer of claim 2, wherein the bulk adhesive layer comprises methylene diphenyl diisocyanate (MDI) resins or poly catechol styrene (PCS).

15. The polymeric layer of any one of claims 11 to 14, wherein the poly-catechol styrene (PCS) has a molecular weight of from about 30,000 to about 90,000.

16. The polymeric layer of claim 14, wherein the ratio of bulk adhesive to PCS is about 90: 10, about 95:5, or about 97.5:2.5.

17. A substrate comprising the polymeric layer of claim 1 disposed on a surface of the substrate.

18. The substrate of claim 17, wherein the substrate comprises a polymeric compound, calcium carbonate, a ceramic, a metal, concrete, stone, reef material, a plastic, a mineral, a composite, a glass, a silane, concrete, wood, reconstituted wood, fiberglass, asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials or combinations thereof; and wherein the substrate is wet, dry, semi -wet or moist.

19. The substrate of claim 17, wherein the substrate is wet.

20. The substrate of claim 17, wherein the substrate is dry.

21. A second substrate in contact with the substrate of claim 16.

22. The second substrate of claim 21, wherein the second substrate is disposed on the polymeric layer.

23. The second substrate of claim 22, wherein the second substrate comprises a polymeric compound, calcium carbonate, a ceramic, a metal, concrete, stone, reef material, a plastic, a mineral, a composite, a glass, a silane, concrete, wood, reconstituted wood, fiberglass, asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials or combinations thereof; and wherein the second substrate is wet, dry, semi -wet or moist.

24. The second substrate of claim 23, wherein the second substrate is wet.

25. The second substrate of claim 23, wherein the second substrate is dry.

26. The second substrate of claim 23, further comprising a second bulk adhesive layer disposed on the polymeric layer.

27. The second substrate of claim 26, wherein the second bulk adhesive layer comprises urethane or a urethane component.

28. A method of making a substrate comprising disposing the polymeric layer of claim 1 on a surface of the substrate.

29. The method of claim 28, wherein the substrate comprises a polymeric compound, calcium carbonate, a ceramic, a metal, concrete, stone, reef material, a plastic, a mineral, a composite, a glass, a silane, concrete, wood, reconstituted wood, fiberglass, asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials or combinations thereof.

30. The method of claim 28, wherein the disposing comprises disposing in a dry environment.

31. The method of claim 30, wherein the dry environment is an ambient environment.

32. The method of claim 30, wherein the disposing comprises disposing in an aqueous environment.

33. The method of claim 32, wherein the aqueous environment is an underwater environment.

34. The method of claim 28, further comprising disposing a bulk adhesive layer on the polymeric layer.

35. The method of claim 34 wherein the bulk adhesive layer comprises urethane or a urethane component.

36. The method of claim 28, further comprising disposing a second substrate on the substrate.

37. The method of claim 36, wherein the second substrate is disposed on the polymeric layer.

38. The method of claim 36, wherein the second substrate comprises a polymeric calcium carbonate, a ceramic, a metal, concrete, stone, reef material, a plastic, a mineral, a composite, a glass, a silane, concrete, wood, reconstituted wood, fiberglass, asphalt, pitch, tar, bitumen, paper, fused materials or agglomerated materials or combinations thereof; and wherein the second substrate is wet, dry, semi -wet or moist.

39. The method of claim 36, wherein the second substrate is wet.

40. The method of claim 36, wherein the second substrate is dry.

41. The method of claim 36, further comprising disposing a second bulk adhesive layer between the second substrate and the polymeric layer.

42. The method of claim 41, wherein the second bulk adhesive layer comprises urethane or a urethane component.

43. A layered structure comprising the polymeric layer of claim 1 disposed between a first substrate and a second substrate.

44. An article comprising the polymeric layer of claim 1.

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