Superhydrophobic coatings, compositions, and methods

Abstract

Disclosed are composite structures including a hydrophobic coating in contact with an aqueous environment. The coating includes a first layer including an amine-functionalized polymer layer having a thickness of 1-500 micrometers and a second layer including a fluoropolymer, a polyolefin, or a combination thereof, and methods of making and repairing the composite structures. A composite adhesive that can be applied as a paint to a surface. These superhydrophobic surfaces are useful for drag reduction in a variety of applications, as antifouling surfaces in marine engineering, and as sealants and gaskets in static applications.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and the benefit of U.S. Provisional Patent Application No. 63 / 283,191, filed November 24, 2021, and entitled “SUPERHYDROPHOBIC COATINGS, COMPOSITIONS AND METHODS,” the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] The present disclosure relates to multi-layer composite structures having a superhydrophobic coating secured (eg, bonded) to a water-resistant adhesive, articles including same, processes for making same, and methods of using same. [Background technology]

[0003] Common polymeric motifs used in adhesives are epoxies, acrylics, and polyurethanes. The effectiveness and strength of adhesion of these conventional adhesives is significantly lower in aqueous environments compared to dry environments. A particularly challenging environment is immersion in a solution, especially one with a non-neutral pH or high ionic content (e.g., brines and other liquids with high concentrations of ions). In aqueous environments in general, especially salt water, surface attachment or adhesion of adhesive materials to substrates is more complicated due to additional interactions between the adhesive and the surface where water and other ions are present.

[0004] Most examples of underwater adhesive technology have been developed based on so-called mussel-inspired adhesives. These are generally based on polymers with a combination of catechol and styrene motifs. See, for example, US Pat. No. 11,046,873 B2. It has been determined that in these systems, modification of the polymer structure is necessary for optimized adhesion in either dry or wet environments. However, a common feature of these adhesives is that they are cured and not reversible. In the event of bond failure or delamination, the substrates cannot be rejoined with the same adhesive strength as when they were originally combined.

[0005] It is known that superhydrophobic surfaces, or surfaces with extremely low surface free energy, are very difficult substrates for adhesion and often have poor mechanical properties that limit their widespread application. See, for example, Zhu, et al. Journal of Materials Chemistry 2011, 21(39), 15793-15797; Chen et al. Advanced Materials Interfaces 2016, 3(6), 1500718.-2. Due to the low surface free energy, these coatings are susceptible to abrasion and other mechanical deformations, and are also difficult to bond to substrates. Thus, fluoropolymers such as PTFE can be used to generate highly desirable surfaces with extreme hydrophobicity or superhydrophobicity, but they are difficult to process as coatings or lubricants due to their low solubility. See, for example, Pradhan, et al. Polymer-Plastics Technology and Materials 2019, 58(5), 498-518. Furthermore, poor adhesion to other surfaces, lack of suitable adhesives that are easy to apply, and lack of suitable adhesives that are environmentally safe have prevented the widespread use of PTFE in many technologically important applications. See, for example, Sheng, et al. Journal of Adhesion 2017, 93(9), 716-733; Jin et al. Macromol. Rapid Commun. 2014, 35(18), 1551-1570.

[0006] There is a significant and growing demand for materials that can coat surfaces and provide enhanced anti-fouling and / or improved wetting behavior. In particular, biofouling and biofilms are costly issues that impact ecological and human health, infrastructure, carbon emissions, and machine performance. For example, in marine environments, biofilms as thin as 50 μm can increase a ship's drag by more than 20%, resulting in significant economic and environmental impacts. In fact, an estimated 70 million tons of additional CO2 are produced by the U.S. Navy as a result of increased fuel consumption due to biofilms. Estimates indicate that fouling in the marine industry in general could generate costs of more than $6.4 billion (U.S.) per year.

[0007] Thus, there is a need for improved adhesives useful with PTFE and other fluoropolymers in hydrophobic and superhydrophobic coatings for drag reduction, as antifouling surfaces in marine engineering, and as sealants and gaskets in static applications. New compositions and processes are also needed to adhere these types of coatings to large and / or irregular substrates, particularly for their use in aqueous environments and marine engineering. The present disclosure addresses these and other unmet needs. Summary of the Invention

[0008] In one embodiment, provided herein is a composite structure comprising a substrate and a hydrophobic coating disposed on a surface of the substrate, the hydrophobic coating comprising a water-resistant adhesive layer comprising an amine-functionalized polymer having a uniform thickness of about 1 μm to about 500 μm, and a hydrophobic layer comprising a fluoropolymer and / or a poly(olefin), preferably wherein the hydrophobic coating is in contact with an aqueous environment / medium.

[0009] In another embodiment, provided herein is a composite structure including a substrate and a coating disposed on a surface of the substrate, the coating including a layer including an amine-functionalized polymer having a uniform thickness of about 1 μm to about 500 μm, and a layer including a fluoropolymer and / or a poly(olefin), preferably a layer where the hydrophobic coating is in contact with an aqueous environment / medium. In some embodiments, the amine-functionalized polymer having a uniform thickness is a water-resistant adhesive. In some embodiments, the amine-functionalized polymer has a uniform thickness of greater than 80 μm. In some embodiments, the amine-functionalized polymer has a uniform thickness of at least 80 μm. In some embodiments, the amine-functionalized polymer has a uniform thickness of 80 μm to 150 μm. In some embodiments, the amine-functionalized polymer has a uniform thickness of at least 150 μm. In some embodiments, the amine-functionalized polymer has a uniform thickness of less than 500 μm. In some embodiments, the amine-functionalized polymer has a uniform thickness of less than 400 μm. In some embodiments, the amine-functionalized polymer has a uniform thickness of less than 300 μm. In some embodiments, the amine-functionalized polymer has a uniform thickness of less than 200 μm. In some embodiments, the coating is a hydrophobic coating. In some embodiments, the layer comprising a fluoropolymer, a poly(olefin), is hydrophobic.

[0010] In a third embodiment, described herein is a process for making a composite structure, the process comprising applying an amine-functionalized polymer layer to a fluoropolymer and / or poly(olefin) to form a coating, and applying the coating to a surface of a substrate to form a composite. In certain embodiments, the process comprises applying an amine-functionalized polymer layer to a fluoropolymer to form a coating. In certain other embodiments, the process comprises applying an amine-functionalized polymer layer to a poly(olefin) to form a coating. In some of these embodiments, the poly(olefin) is selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), and polypropylene (PP). In some examples, the poly(olefin) is HDPE. In some other examples, the poly(olefin) is LDPE. In some examples, the poly(olefin) is PP.

[0011] In a fourth embodiment, provided herein is a process for making a composite structure, the process comprising applying an amine-functionalized polymer layer to a surface of a substrate and applying a fluoropolymer or a poly(olefin) to the amine-functionalized polymer layer. In certain embodiments, the process comprises applying a fluoropolymer to the amine-functionalized polymer layer. In certain other embodiments, the process comprises applying a poly(olefin) to the amine-functionalized polymer layer.

[0012] In a fifth embodiment, presented herein is a process for making a composite structure, comprising applying an amine-functionalized polymer layer to a surface of a substrate and applying a polyurethane or epoxy-based paint to the amine-functionalized polymer layer. In certain embodiments, the paint may include an additive to increase hydrophobicity. In some of these embodiments, the additive includes a fluoropolymer additive. In some examples, the fluoropolymer is a PTFE particle. In some of these examples, the fluoropolymer is a PTFE particle having a particle size P, where 0.001 mm≦P≦0.1 mm. In some of these examples, the fluoropolymer is a PTFE particle having a particle size greater than 0.001 mm. In some of these examples, the fluoropolymer is a PTFE particle having a particle size greater than 0.1 mm. In some of these examples, the fluoropolymer is a PTFE particle having a particle size less than 1 mm.

[0013] In a sixth embodiment, presented herein is a process for making a composite structure, the process comprising applying an amine-functionalized polymer layer to a surface of a substrate and applying a fluoropolymer-based aerosol spray to the amine-functionalized polymer layer.

[0014] In a seventh embodiment, provided herein is a process for repairing a composite structure comprising providing, or having provided, a composite structure as disclosed herein, the composite structure having a defect, and applying pressure to repair the defect.

[0015] In an eighth embodiment, provided herein is a method of making a composite structure, the method comprising: a. applying an amine-functionalized polymer layer to a surface of a substrate; b. applying the amine-functionalized polymer layer to a fluoropolymer and / or poly(olefin) to form a coating; and b. bonding the amine-functionalized polymer layer to form a composite. [Brief description of the drawings]

[0016] [Figure 1] 1 is a plot of peel strength as a function of external conditions. [Diagram 2] 1 is a plot of lap shear strength as a function of external conditions. [Diagram 3] 1 is a plot of peel strength as a function of external conditions. [Figure 4] 1 is a plot of peel strength as a function of external conditions. [Diagram 5] 1 is a plot of lap shear strength as a function of external conditions. [Figure 6] 1 is a plot of peel strength as a function of external conditions. [Figure 7(a)] 1 is a photograph of a steel panel coated with an amine-functionalized polymer. [Figure 7(b)] Photograph of a steel panel coated with an amine-functionalized polymer followed by an antifouling paint. [Figure 7(c)] Photograph of a steel panel coated with an amine-functionalized polymer followed by a polyurethane paint. [Figure 8] The left side shows the amine-functionalized polymer sprayed onto an aluminum (Al) sheet, and the right side shows DuPont Teflon® aerosol sprayed as a topcoat onto the amine-functionalized polymer coating. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] Provided herein are composite structures having hydrophobic, and in some embodiments superhydrophobic, coatings, articles including such composite structures, and methods of making and using such compositions. The composite structures, in some embodiments, include a substrate and a coating disposed on a surface of the substrate. In some examples, the coating is hydrophilic. In other examples, the coating is hydrophobic. The coating, in some embodiments, includes an adhesive layer including an amine-functionalized polymer and a hydrophobic layer including a fluoropolymer or poly(olefin). In some embodiments, the substrate may be primed or unprimed, may be large, irregular, and / or non-uniform. In other embodiments, the substrate may be unmodified or may be pretreated with another coating. In other embodiments, the substrate may be unmodified or may be pretreated with another coating, may be large, irregular, and / or non-uniform. In some embodiments, the substrate is pretreated by a physical method. In some of these embodiments, the physical method includes, but is not limited to, sandblasting, grit blasting, sand abrasion, or grit abrasion. The hydrophobic coatings, and by extension the composite structures and / or articles described herein, exhibit anti-wetting, anti-fouling, and self-healing properties and are useful in a variety of applications including, but not limited to, drag reduction, anti-fouling surfaces in marine engineering, and sealants and gaskets in static applications. The hydrophobic coatings, and by extension the composite structures and / or articles described herein, can be used to prevent water and ice from wetting or adhering to the surface of the material, reducing or preventing corrosion and marine biofouling.

[0018] As used herein, the term "hydrophobic" means and includes any material or surface on which a drop of water has a contact angle in air of at least 90° as measured by a contact angle goniometer as described in ASTM D7334-08. Additionally, as used herein, the term "superhydrophobic" means and includes any material or surface on which a drop of water has a contact angle in air of at least 150° as measured by a contact angle goniometer as described in ASTM D7334-08. Thus, "superhydrophobic" materials are also considered to be "hydrophobic", however, a "hydrophobic" material may not necessarily be "superhydrophobic" in certain embodiments. In various embodiments, the hydrophobic coating of the present invention can include a contact angle in air of at least or about 90°, at least or about 100°, at least or about 110°, at least or about 120°, at least or about 130°, at least or about 140°, at least or about 150°, at least or about 160°, or at least or about 170°. In various embodiments, the hydrophobic coating of the present invention can include a contact angle in air of 120°. In various embodiments, the hydrophobic coating of the present invention can include a contact angle in air of 110-130°.

[0019] As used herein, "substrate" refers to flexible substrates, rigid substrates, and substrates made from, including, consisting of, or consisting essentially of poly(tetrafluoro)ethylene (PTFE), polyolefins, metals (e.g., steel), metal composites, carbon fiber, peelable films, wood, fiberglass, composites, glass, rubber, ceramics, adhesive films, paints, ship hulls, submarines, offshore floating structures, fishing / aquaculture equipment, fishing / aquaculture equipment, pipes / pipelines, drilling rigs, floating buoys, storage vessels, any surface in contact with an aqueous environment, air / refrigeration systems and ducts, dams, bridges, and other civilian structures.

[0020] Suitable fluoropolymers used to provide hydrophobic coatings include, for example, polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoroalkoxy polymers (PFA), fluorinated ethylene-propylene (FEP), ethylene tetrafluoroethylene (ETFE), and related perfluoroelastomers. In embodiments, the PTFE can be a porous unsintered film or a thermally annealed sintered film. Suitable poly(olefins) for use in the present invention include polypropylene (PP), polyethylene (PE), polybutadiene (PBD), polystyrene (PS), polyvinyl chloride (PVC), and combinations thereof. In embodiments, the hydrophobic coating can include a combination of a fluoropolymer and a polyolefin. See, for example, (ACS Appl. Mater. Interfaces 2016, DOI:10.1021 / acsami.5b12165). In some examples, the PTFE is a derivative of PTFE. In certain embodiments, the fluoropolymer is PTFE. In certain other embodiments, the fluoropolymer is PVF. In certain other embodiments, the fluoropolymer is PVDF. In certain other embodiments, the fluoropolymer is PCTFE. In certain other embodiments, the fluoropolymer is PFA. In certain other embodiments, the fluoropolymer is FEP. In certain other embodiments, the fluoropolymer is ETFE. In certain other embodiments, the fluoropolymer is PVF. Porous unsintered and / or thermally annealed PTFE can be purchased commercially. For example, the material is available from Saint Gobain (https: / / www.plastics.saint-gobain.com / ). See part numbers #128060WHT-FW and #SF00000540000C.

[0021] In some other embodiments, the hydrophobic / superhydrophobic coating applied to the adhesive layer (e.g., the amine-functionalized polymer layer) is a paint or similar type of coating. In some of these embodiments, the hydrophobic / superhydrophobic coating is a paint and not simply a fluoropolymer or polyolefin film.

[0022] In some embodiments, described herein are multi-layer composites. In some of these embodiments, one layer of the multi-layer composite is a layer comprising steel. In some of these embodiments, the next adjacent layer is an amine-functionalized polymer. In some of these embodiments, adjacent to the amine-functionalized polymer is a third layer that is a paint coating layer.

[0023] In some embodiments, described herein are multi-layer composites. In some of these embodiments, one layer of the multi-layer composite is a layer comprising steel. In some of these embodiments, the next adjacent layer is an amine-functionalized polymer. In some of these embodiments, adjacent to the amine-functionalized polymer is a third layer that is a spray-coated layer.

[0024] In some embodiments, described herein are multi-layer composites. In some of these embodiments, one layer of the multi-layer composite is a layer that includes steel. In some of these embodiments, the next adjacent layer is an amine-functionalized polymer. In some of these embodiments, adjacent to the amine-functionalized polymer is a third layer that is a layer made from Teflon® aerosol.

[0025] In some embodiments, described herein are multi-layer composites. In some of these embodiments, one layer of the multi-layer composite is a layer comprising steel. In some of these embodiments, the next adjacent layer is an amine-functionalized polymer. In some of these embodiments, adjacent to the amine-functionalized polymer is a third layer that is a layer made from PTFE (Teflon®).

[0026] In some embodiments, including any of the above, PTFE is included as an additive in a paint coating, see, for example, the paints at https: / / www.international-marine.com / product / intersleek-1100sr (these paints are incorporated herein by reference for all purposes).

[0027] The substrate can be formed from any material known in the art, such as plastic, glass, fused silica, fiberglass, ceramic, metal, wood, fabric, carbon fiber, fabric and textile, and the like. Examples of suitable substrates include polymeric substrates, such as polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), polycarbonate (PC), polyurea (PU), or combinations thereof, glass substrates, or metal substrates, such as steel (e.g., mild steel containing 0.15% to 0.23% carbon) or aluminum alloy, or combinations thereof. The substrate can also include concrete. The substrate can be of any configuration configured to facilitate the formation of a coating suitable for use in a particular application. In an exemplary embodiment, the substrate can be a peelable film. In certain embodiments, the substrate is steel. In certain other embodiments, the substrate is polyethylene. In certain embodiments, the substrate is concrete.

[0028] In certain embodiments, the hydrophobic coatings (and by extension, the composite structures and articles described herein) exhibit both hydrophobic and oleophobic properties. In certain embodiments, the hydrophobic coatings (and by extension, the composite structures and articles described herein) exhibit oleophobic properties. In certain embodiments, the hydrophobic coatings (and by extension, the composite structures and articles described herein) exhibit hydrophobic properties. Coatings with a surface tension lower than water (72 mN / m) but higher than oil (20-30 mN / m) can attract oil (oleophilic) but repel water, whereas coatings with low surface tension (about 20 mN / m or less) can repel both oil (oleophobic) and water, making them useful for anti-fouling, such as in medical and transportation applications. Thus, these articles can exhibit a variety of desirable properties, such as, for example, self-cleaning, anti-fouling, anti-smudge, and anti-icing properties. In some embodiments, the coating can provide microbial resistance to the article, moisture resistance to the article (e.g., metal surfaces or other surfaces including wood or ceramic surfaces), anti-fouling properties to the article (e.g., surfaces, filters, membranes, or actuators). In some embodiments, including any of the above, the coating can reduce friction and drag. In some embodiments, including any of the above, the coating can provide a seal (e.g., a sealing valve). In some embodiments, including any of the above, the article can be an amphibious or personal surface vessel (e.g., a ship, boat, submarine, or jet ski), or other floating and / or underwater device (e.g., a buoy, dock, or drilling rig), an implantable device (e.g., a biochip, biosensor, or other medical device), an electrical device (rigid and stretchable printed circuit boards, communication devices, etc.), a pipeline, building and construction materials, apparel, or textiles.

[0029] In some embodiments, including any of the above, the amino-functionalized polymers herein may be used as an adhesive layer between a superhydrophobic surface and another surface.

[0030] In some embodiments, including any of the above, the amino-functionalized polymers herein can be used to prime the surface of another substrate and a third layer applied to the primed surface.

[0031] In some embodiments, including any of the above, the amino-functionalized polymers herein may be used to promote adhesion between two substrates, one of which is a superhydrophobic surface. In some embodiments, including any of the above, this adhesion occurs in water.

[0032] In some embodiments, including any of the above, the multi-layer structure comprising an amino-functionalized polymer and a superhydrophobic surface herein may be self-healing. In some embodiments, including any of the above, the multi-layer structure comprising an amino-functionalized polymer and a superhydrophobic surface herein may be used as a gap-filling material. In some of these embodiments, including any of the above, if the multi-layer structure comprising an amino-functionalized polymer and a superhydrophobic surface is damaged, the multi-layer structure may be repaired by applying pressure on the multi-layer structure. In some embodiments, the pressing is accomplished using pressure applied by a human hand.

[0033] In some embodiments, including any of the above, the uniform thickness is less than about 500 μm, less than about 450 μm, less than about 400 μm, less than about 350 μm, less than about 300 μm, or less than about 250 μm.

[0034] In some embodiments, including any of the above, the uniform thickness is at least 200 μm.

[0035] In some embodiments, including any of the above, the uniform thickness is between about 10 μm and 400 μm, between about 25 μm and about 300 μm, between about 50 μm and 250 μm, or between about 75 μm and 125 μm.

[0036] In some embodiments, including any of the above, the adhesive layer is a film having a film thickness of from 100 μm to 400 μm.

[0037] In some embodiments, including any of the above, the adhesive layer is a film having a film thickness of from 75 μm to 125 μm.

[0038] In some embodiments, including any of the above, the hydrophobic layer is a film having a film thickness of from 1 μm to 500 μm.

[0039] In some embodiments, including any of the above, the hydrophobic layer is a film having a film thickness of between 75 μm and 125 μm.

[0040] In some embodiments, including any of the above, the hydrophobic layer is a film having a film thickness of greater than 400 μm.

[0041] In some embodiments, including any of the above, the uniform thickness is between 100 μm and 400 μm.

[0042] In some embodiments, including any of the above, the uniform thickness is between 75 μm and 125 μm.

[0043] In some embodiments, including any of the above, the uniform thickness is between 1 μm and 500 μm.

[0044] In some embodiments, including any of the above, the uniform thickness is between 75 μm and 125 μm.

[0045] In some embodiments, including any of the above, the uniform thickness is greater than 400 μm.

[0046] Suitable amine-functionalized polymers for use in the present disclosure include those disclosed in co-pending International Patent Application Nos. PCT / CA2018 / 050619, PCT / CA2019 / 050704, and PCT / CA2018 / 050046, the disclosures of which are expressly incorporated herein by reference.

[0047] Suitable amine-functionalized polymers for use in the present disclosure include those disclosed in U.S. Patent Application Publication No. US20210214542A1, the disclosure of which is expressly incorporated herein by reference.

[0048] Suitable amine-functionalized polymers for use in the present disclosure include: (a) Gilmour, DJ; Tomkovic, T.; Kuanr, N.; Perry, MR; Gildenast, H.; Hatzikiriakos, SG; Schafer, LL, Catalytic Amine Functionalization and Polymerization of Cyclic Alkenes Creates Adhesive and Self-Healing Materials. ACS Applied Polymer Materials 2021, 3, 2330-2335; (b) Kuanr, N.; Gilmour, DJ; Gildenast, H.; Perry, MR; Schafer, LL, Amine-Containing Monomers for Ring-Opening Metathesis Polymerization: Understanding Chelate Effects in Aryl- and Alkylamine-Functionalized Polyolefins. Macromolecules 2022, (c) Yavitt, BM; Tomkovic, T.; Gilmour, DJ Zhang, Z.; Kuanr, N.; van Ruymbeke, E.; Schafer, LL; and Hatzikiriakos, SG, Rheology and self-healing of amine functionalized polyolefins. Journal of Rheology, 2022, 66, 1125-1137, the disclosures of which are expressly incorporated by reference.

[0049] Briefly, in embodiments, the subject amine-functionalized polymers comprise an amine-functionalized compound of formula 2: [ka] (wherein (---) represents an optional double bond; M 1 and M 2 are independently -OH, substituted or unsubstituted C 1~15 an alkyl, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 are independently H or CH3; Each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 are independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, -C(=O)R', or -C(OR')R'', Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 At least one of the following is -CR 1 R 2 -NR 3 R 4 and R', R'', R 1 , R 2 , R 3 and R 4 each is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; where n is a natural number greater than 1 and less than 10,000,000,000).

[0050] An embodiment of the present disclosure is a polymer formed by radical or anionic polymerization of the amine-functionalized compound described above, wherein the functional end group M of the amine-functionalized compound is 1 and M 2 and a polymer which functions as an initiation point.

[0051] A prepared block copolymer comprising an amine-functionalized compound as described above and at least one additional polymer.

[0052] In embodiments, the subject amine-functionalized polymers include amine-functionalized compounds of formula 3: [ka] (wherein (---) represents an optional double bond; M 1 and M 2 are independently -OH, substituted or unsubstituted C 1~15 an alkyl, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 are independently H or CH3; Each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4are independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, -C(=O)R', or -C(OR')R'', Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 At least one of the following is -CR 1 R 2 -NR 3 R 4 and R', R'', R 1 , R 2 , R 3 and R 4 each is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers, The monomers may comprise, consist of, or consist essentially of a cyclic alkyl group (in which the monomers are connected in a head-to-head manner).

[0053] In embodiments, the subject amine-functionalized polymers include an amine-functionalized compound of formula X: [ka] (wherein (---) represents an optional double bond; M 1 and M 2 are independently -OH, substituted or unsubstituted C 1~15 an alkyl, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3, and X 4 are independently H or CH3; Each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Z 1 , Z 2 , Z 3 , and Z 4 are independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, -C(=O)R', or -C(OR')R'', Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 At least one of the following is -CR 1 R 2 -NR 3 R 4 and R', R'', R 1 , R 2 , R 3 and R 4 each is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; where n and m are natural numbers.

[0054] In embodiments, the subject amine-functionalized polymers include amine-functionalized compounds of formula 6: [ka] (wherein (---) represents an optional double bond; each X 1 , X 2 , X 3 , and X 4 are independently H or CH3; Each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 are independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, -C(=O)R', or -C(OR')R'', Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 At least one of the following is -CR 1 R 2 -NR 3 R 4 and R', R'', R 1 , R 2 , R 3 and R 4 each is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; wherein r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2.

[0055] An aspect of the present disclosure is a brush copolymer comprising the above-mentioned polymer and polymeric bristles or brushes, 1 , X2 , X 3 , X 4 , Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , Z 4 , R', R'', R 1 , R 2 , R 3 , and R 4 for brush copolymers, at least one of which serves as a starting point for subsequent synthesis of polymeric bristles or brushes.

[0056] In certain embodiments, including any of the foregoing, the compound of formula 2 is 3 or Y 4 A-CR 1 R 2 -NR 3 R 4 R 3 or R 4 is each independently substituted or unsubstituted aryl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0057] In certain embodiments, including any of the foregoing, the compound of formula 6 is 3 or Y 4 A-CR 1 R 2 -NR 3 R 4 where R 3 or R 4 is each independently substituted or unsubstituted aryl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0058] In certain embodiments, including any of the foregoing, the compound of formula 2 is 3 or Y 4 A-CR 1 R 2 -NR 3 R 4 R 3 or R 4 are each independently substituted or unsubstituted phenyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0059] In certain embodiments, including any of the foregoing, the compound of formula 6 is 3 or Y 4 A-CR 1 R 2 -NR 3 R 4 where R 3 or R 4 are each independently substituted or unsubstituted benzyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0060] In certain embodiments, including any of the foregoing, the compound of formula 2 is 3 or Y 4 A-CR 1 R 2 -NR 3 R 4 where R 3 or R 4 is phenyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0061] In certain embodiments, including any of the foregoing, the compound of formula 6 is 3 or Y 4 A-CR 1 R 2-NR 3 R 4 where R 3 or R 4 is benzyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0062] In certain embodiments, including any of the foregoing, the compound of formula 2 is 3 or Y 4 A-CR 1 R 2 -NR 3 R 4 where R 3 and R 4 are both phenyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0063] In certain embodiments, including any of the foregoing, the compound of formula 6 is 3 or Y 4 A-CR 1 R 2 -NR 3 R 4 where R 3 and R 4 are both benzyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0064] In some embodiments, Y 3 or Y 4 is CH2-NH-Ph, where Ph is phenyl. In some other embodiments, q is 1 and r is 0.

[0065] In some embodiments, Y 3 or Y 4is CH2-NH-Ph-F, where Ph is phenyl. In some other embodiments, q is 1 and r is 0.

[0066] In some embodiments, Y 3 or Y 4 is CH2-NH-Ph-OH3, where Ph is phenyl. In some other embodiments, q is 1 and r is 0.

[0067] An aspect of the present disclosure relates to an amine-functionalized polyalkylene or polyalkane, the polyalkylene or polyalkane being [ka] [ka] is or contains where n is a natural number greater than 1 and less than 500,000. In some embodiments, n is less than 100,000.

[0068] In some embodiments, the amine-functionalized polyalkylene or polyalkane is [ka] is or contains

[0069] In some embodiments, the amine-functionalized polyalkylene or polyalkane is [ka] is or contains

[0070] An embodiment of the present disclosure relates to a copolymer comprising a mixture of different amine-functionalized monomer units of formula 5: [ka] In the formula, M 1 and M2 are -OH, substituted or unsubstituted C, respectively. 1~15 is selected from an alkyl, a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, or a functionalized end group suitable for ring-opening metathesis polymerization; X 1 , X 2 , X 3 , and X 4 each is independently H or CH; Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Z 1 , and Z 2 each is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, -C(=O)R', or -C(OR')R'', R', R'', R a , R 1 , R 2 , R 3 , and R 4 each is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protecting group; R' or R'' is -CR 1 R 2 -NR 3 R 4 and r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n is a natural number greater than 1. In some embodiments, n is less than 100,000,000.

[0071] In embodiments, the subject amine-functionalized polymers may comprise, consist of, or consist essentially of the following amine-functionalized compounds: [ka] where the subscript n is an integer greater than 1 and less than 100,000,000,000. In some embodiments, n is less than 100,000.

[0072] In embodiments, the subject amine-functionalized polymers have, as a portion of the polymer, the following structure: [ka] wherein the subscript n is an integer greater than 1 and less than 100,000,000,000. In some embodiments, n is less than 100,000. EXAMPLES

[0073] F. Working Example Polymer synthesis Poly(aminocyclooctene) was prepared according to published methods (Gilmour, DJ et al. ACS Applied Polymer Materials 2021,3(5),2330-2335.). Briefly, poly(aminocyclooctene) is prepared via ring-opening metathesis polymerization (ROMP) of amine-functionalized cyclooctene monomers, followed by hydroaminoalkylation of cyclooctadiene with secondary methylamines, e.g., N-methylaniline. The polymer was isolated and purified according to published protocols. Polymer solutions for spray application were prepared by dissolving the material in a suitable carrier solvent, e.g., dichloromethane.

[0074] Polymer characterization The polymers were analyzed by conventional chemical characterization techniques for polymers, including NMR spectroscopy, IR spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). 1H NMR spectra were collected using a Bruker Avance instrument operating at 300 or 400 MHz. IR spectra were recorded at room temperature on a Perkin Elmer FTIR equipped with an ATR accessory for direct measurements of oils and polymeric materials. Polymer Mn, Mw and dispersity [ka] were obtained using triple detection gel permeation chromatography (GPC). All GPC characterizations were performed in HPLC grade THF at a flow rate of 1.0 mL / min using a Malvern OMNISEC GPC instrument equipped with a Viscotek TGuard guard column (CLM3008) and Viscotek T3000 (CLM3003) and T6000 (CLM3006) GPC columns filled with porous poly(styrene-co-divinylbenzene) particles conditioned at room temperature. The instrument was equipped with triple detection to achieve signal response from a differential viscometer, a differential refractive index detector, and right-angle and low-angle light scattering detectors. Thermal properties of the samples were measured with a Netzsch DSC 214 Polyma differential scanning calorimeter. A Netzsch TG 209 F1 Libra® thermogravimetric analyzer was used for the thermogravimetric experiments.

[0075] Adhesive properties Adhesion was quantified using a Dynamic Mechanical Analyzer (DMA, RSA G2 TA Instruments) equipped with a tensile fixture to perform peel strength measurements. A solution of the polymer was applied between the two substrates via spray and after drying, the two sheets of PTFE were brought into contact by hand with minimal pressure. Specimens were prepared according to DMA instrument specifications with a width of 6 mm and a length of 17 mm. An unbonded peel arm was clamped onto the tension fixture using an untreated tab of 20 mm length. A constant peel rate of 10 mm / min at room temperature was applied in axial mode. The test was repeated 10 times.

[0076] Samples for wetting tests were prepared and tested on HDPE (BCT-195357 Exxon) and PTFE (08277-15 5mil Skived Cole Parmer). The polymer samples were dissolved in dichloromethane to obtain approximately 7.5% by weight (m / v) solutions. Immediately after preparing the bonded samples, they were immersed in the given solutions (distilled water, seawater, 8M HCl, 8M NaOH) for 21 days. After storage, the samples were analyzed for adhesion properties using a DMA equipped with an immersion cell.

[0077] Example 1 Formulation: An optimized spray application process by varying the solution viscosity and concentration to obtain adhesive films of various thicknesses. The optimal solution viscosity and concentration were determined to obtain homogeneous (i.e. even) films. The film thickness threshold at which maximum adhesive strength was reached was determined.

[0078] The thickness may be controlled by the amount of material deposited.

[0079] Ability to apply adhesive to underwater substrates. Polymer solutions can be delivered using a syringe or other delivery method to a substrate that is underwater and can then adhere to a second substrate when coated. Samples can also be prepared under dry conditions and then immersed in the solution.

[0080] Remarkably, as demonstrated for the first time herein, the subject adhesives can be reversibly applied and / or reused. When bonded objects are separated, they can "self-heal" or recombine to recreate the original adhesive strength when first bonded. This feature is achieved by the combination of the adhesive and self-healing properties of the polymers.

[0081] HDPE specimens bonded using polymer adhesives showed no difference in T peel force when stored in deionized water or seawater compared to dry conditions. For PTFE specimens, the T peel force for dry and deionized immersion was approximately equal within experimental error, but storage in seawater resulted in a slight increase in T peel force. In the lap shear configuration, no significant difference was observed for HDPE, while for PTFE, a slight increase in lap shear strength was observed for specimens immersed in deionized water or seawater. Without being bound by theory, it is possible that in seawater, the presence of ions and inorganic particles such as salts, metals, etc., may result in an enhancement of the adhesive strength of the polymer, possibly by ion chelation mediated crosslinking. Since the adhesive failure mode is observed to be adhesive to adhesive failure, this indicates that the strength of the adhesion at the interface of the polymer and substrate is greater than that of the tensile strength of the material. Since an adhesive failure mode is observed for specimens under immersion, it suggests that the presence of ions at the surface does not reduce surface adhesion. See Figures 1 and 2.

[0082] Example 2 A very challenging environment for traditional adhesives is a highly acidic or alkaline environment. HDPE and PTFE samples were prepared and tested after immersion in highly acidic or highly alkaline solutions and compared to a dry environment control. For both PTFE and HDPE, a slight increase in T-peel and lap shear adhesion was observed after storage in alkaline conditions. In acidic solutions, a significant increase in T-peel and lap shear adhesion was observed after immersion. Without being bound by theory, it is believed that the amine groups of the polymer adhesive can promote ionic interactions with hydronium ions in solution, which may lead to increased adhesion strength. See Figures 3 and 4.

[0083] The polymer adhesive was also applied to raw untreated steel coupons and tested in a shear lap configuration. Storage in seawater led to a significant increase in lap shear strength. It is hypothesized that corrosion initiation occurs rapidly on the steel in seawater and iron ions released from corrosion of the steel lead to an enhanced increase in peel strength due to metal ion chelation. This suggests that improved adhesion can be obtained in the presence of a corrosive environment. See Figure 5.

[0084] A comparison was also made with the performance of a commercial adhesive (LePage Plastic Bonder) under soaking conditions. Visually, the samples appeared to deteriorate and, unlike the present invention, the samples could not be rebonded after delamination. See Figure 6.

[0085] Example 3 This example is a process for using a multi-layer amine-functionalized polymer and a commercial paint coating.

[0086] Multi-layer amine-functionalized polymer-commercial paint coatings were obtained by first applying the amine-functionalized polymer via a dissolved solution of the polymer in dichloromethane (concentration = 75 mg / ml) using a spray process on P110 steel panels with dimensions of 8" x 24". After spraying, the amine-functionalized polymer coating was allowed to dry at room temperature for at least 24 hours before applying the commercial paint. The amine-functionalized polymer coating had a thickness of about 0.1 mm. Two commercial paint systems have been demonstrated: AkzoNobel Interlux® Bottomkote® XXX antifouling paint, and Epifanes polyurethane two-component Yacht coating. The commercial paint was applied onto the amine-functionalized polymer coated steel panels using a paint brush according to the product application specifications. After application, the coated panels were allowed to dry at room temperature for at least 48 hours before being immersed.

[0087] The results are shown in Figures 7(a), 7(b), and 7(c).

[0088] Amine-functionalized polymer bottom coat - DuPont Teflon® spray top coat: The amine-functionalized polymer (0.1 mm thick) was first sprayed onto a 6" x 6" flat aluminum sheet. After the coating was allowed to dry at room temperature for 24 hours, DuPont anti-block dry film lubricant with Teflon® fluoropolymer aerosol was sprayed onto the amine-functionalized polymer coating. The entire amine-functionalized polymer coating was covered with Teflon® spray and allowed to dry for 24 hours.

[0089] The results are shown in Figure 8.

[0090] The above-described embodiments and examples are intended to be merely illustrative and non-limiting. Those skilled in the art will recognize, or be able to ascertain using only routine experimentation, numerous equivalents of the specific compounds, materials, and procedures. All such equivalents are considered to be within the scope and are encompassed by the appended claims. Furthermore, only certain representative materials and method steps disclosed herein are specifically described, but other combinations of materials and method steps are also intended to be within the scope of the appended claims even if not specifically recited. Thus, although a combination of steps, elements, components, or ingredients may be explicitly described herein, other combinations of steps, elements, components, and ingredients are included even if not explicitly described.

[0091] As used herein, the term "comprises" and variations thereof are used synonymously with the term "including" and variations thereof and are open, non-limiting terms. The terms "comprises" and "includes" are used herein to describe various embodiments, but the terms "consisting essentially of" and "consisting of" may be used in place of "comprises" and "includes" to provide more specific embodiments and are disclosed. As used in this disclosure and the appended claims, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise.

Claims

1. A composite structure comprising a substrate and a hydrophobic coating disposed on a surface of the substrate, the hydrophobic coating comprises a layer comprising an amine-functionalized polymer having a uniform thickness of about 1 μm to about 500 μm and a layer comprising a fluoropolymer, a poly(olefin), or a combination thereof; The composite structure wherein the hydrophobic coating is in contact with an aqueous environment / medium.

2. The composite structure of claim 1 , wherein the hydrophobic coating is immersed in and / or submerged in the aqueous environment / medium.

3. 3. The composite structure of claim 1 or 2, wherein the fluoropolymer is selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoroalkoxy polymers (PFA), fluorinated ethylene-propylene (FEP), and related perfluoroelastomers.

4. 4. The composite structure of any one of claims 1 to 3, wherein the poly(olefin) is selected from the group consisting of polypropylene (PP), polyethylene (PE), polybutadiene (PBD), polystyrene (PS), polyvinyl chloride (PVC), and combinations thereof.

5. The composite structure of any one of claims 1 to 4, wherein the substrate is the hull of a boat, ship, submarine, or personal watercraft.

6. The composite structure of any one of claims 1 to 5, wherein the substrate is flexible.

7. The composite structure of any one of claims 1 to 6, wherein the substrate is rigid.

8. 8. The composite structure of any one of claims 1 to 7, wherein the substrate is a release film, and optionally the release film is polydimethylsiloxane (PDMS), PDMS / silicone, silicone, vinyl adhesive, or a combination thereof.

9. 9. The composite structure of any one of claims 1 to 8, wherein the substrate comprises a secondary coating layer, optionally the secondary coating layer comprises a secondary adhesive, a paint primer, or a coating that protects the hull; and the secondary adhesive is selected from the group consisting of polyurethane, acrylic, cyanoacrylate, and epoxy.

10. 10. The composite structure of claim 9, wherein the coating protecting the hull is a scratch resistant layer or a barrier coating for corrosion and fouling resistance.

11. An article comprising the composite structure of any one of claims 1 to 10, wherein the article is in contact with or immersed in an aqueous environment.

12. 12. The article of claim 11, wherein the article is a boat, a ship, a submarine, a personal watercraft, a buoy, a dock, or a drilling rig.

13. 1. A method of making a composite structure, comprising: a. applying an amine-functionalized polymer layer to a fluoropolymer and / or poly(olefin) to form a coating; b. applying the coating to a surface of a substrate to form a composite; The method, wherein the amine-functionalized polymer is a compound of Formula 2, Formula 3, Formula X, or Formula 6: 【Chemistry 1】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n is a natural number greater than 1 and less than 10,000,000,000), 【Chemistry 2】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers, The monomers are connected in a head-to-head fashion. 【Transformation 3】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers) 【Chemistry 4】 (wherein (----) represents an optional double bond, each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2).

14. 1. A method of making a composite structure, comprising: a. applying an amine-functionalized polymer layer to the surface of a substrate; b. applying a fluoropolymer or poly(olefin) to the amine-functionalized polymer layer, wherein the amine-functionalized polymer is a compound of Formula 2, Formula 3, Formula X, or Formula 6: 【Transformation 5】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n is a natural number greater than 1 and less than 10,000,000,000), 【Transformation 6】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers, The monomers are connected in a head-to-head fashion. 【Transformation 7】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers) 【Transformation 8】 (wherein (----) represents an optional double bond, each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2).

15. 1. A method of making a composite structure, comprising applying a combination of an amine-functionalized polymer and a fluoropolymer and / or a poly(olefin) to a surface of a substrate, wherein the amine-functionalized polymer is a compound of Formula 2, Formula 3, Formula X, or Formula 6: 【Chemistry 9】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n is a natural number greater than 1 and less than 10,000,000,000), 【Chemistry 10】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers, The monomers are connected in a head-to-head fashion. 【Chemistry 11】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers) 【Chemistry 12】 (wherein (----) represents an optional double bond, each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2).

16. 1. A method of making a composite structure, comprising: c. applying an amine-functionalized polymer layer to the surface of the substrate; d. applying a paint coating to the amine-functionalized polymer layer, wherein the amine-functionalized polymer is a compound of Formula 2, Formula 3, Formula X, or Formula 6: 【Chemistry 13】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n is a natural number greater than 1 and less than 10,000,000,000), 【Chemistry 14】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers, The monomers are connected in a head-to-head fashion. 【Chemistry 15】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers) 【Chemistry 16】 (wherein (----) represents an optional double bond, each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2).

17. 1. A method of making a composite structure, comprising: a. applying an amine-functionalized polymer layer to the surface of a substrate; b. applying an amine-functionalized polymer layer to a fluoropolymer, a poly(olefin), or a combination thereof to form a coating; b. bonding the amine-functionalized polymer layer to form a composite, wherein the amine-functionalized polymer is a compound of Formula 2, Formula 3, Formula X, or Formula 6: 【Chemistry 17】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n is a natural number greater than 1 and less than 10,000,000,000), [Chemistry 18] (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers, The monomers are connected in a head-to-head fashion. 【Chemistry 19】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers) 【Chemistry 20】 (wherein (----) represents an optional double bond, each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2).

18. The composite structure of any one of claims 1 to 12, wherein the amine-functionalized polymer is a compound of Formula 2, Formula 3, Formula X, or Formula 6: 【Chemistry 21】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n is a natural number greater than 1 and less than 10,000,000,000), 【Chemistry 22】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers, The monomers are connected in a head-to-head fashion. 【Chemistry 23】 (wherein (----) represents an optional double bond, M 1 and M 2 are independently —OH, substituted or unsubstituted C 1-15 alkyl, substituted or unsubstituted aromatic ring, substituted or unsubstituted heterocycle, or a functional end group suitable for ring-opening metathesis polymerization; each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 , Y 11 , Y 12 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2; n and m are natural numbers) 【Chemistry 24】 (wherein (----) represents an optional double bond, each X 1 , X 2 , X 3 , and X 4 is independently H or CH 3 ; each Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, an amine-compatible protecting group, —C(═O)R′, or —C(OR′)R″; and at least one of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Z 1 , Z 2 , Z 3 , and Z 4 is —CR 1 R 2 —NR 3 R 4 ; each of R', R'', R 1 , R 2 , R 3 and R 4 is independently H, substituted or unsubstituted linear or cyclic alkyl or alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocycle, or an amine-compatible protecting group; r=0 or 1, and q=0 or 1, and r+q=0, 1, or 2).

19. The composite structure of any one of claims 1 to 12, wherein the amine-functionalized polymer is or comprises: 【Chemistry 25】 【Chemistry 26】 (where n is a natural number greater than 1 and less than 500,000. In some embodiments, n is less than 100,000).

20. The method of any one of claims 13-17, wherein the amine-functionalized polymer is or comprises: 【Chemistry 27】 【Chemistry 28】 (where n is a natural number greater than 1 and less than 500,000. In some embodiments, n is less than 100,000).

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