Industrial-scale method for forming a covalently bonded monomer and graphene oxide structure

Abstract

The present invention relates to a method of making a chemisorbed graphene oxide polymer composite, the method comprising the steps of placing a monomer and graphene oxide in a ball mill; grinding the monomer with a carbon additive to produce a physisorbed monomeric graphene oxide material; placing the physisorbed monomeric graphene oxide material in a polymerization chemical reactor to convert the physisorbed monomeric graphene oxide to chemisorbed monomeric graphene oxide; and reacting the monomeric carbon additive with other monomers or prepolymers to polymerize the material to form a chemisorbed carbon polymer composite.

Description

Technical Field

[0001] Cross - References to Related Applications This PCT international patent application claims priority to U.S. Provisional Patent Application No. 62 / 732,723, filed on September 18, 2018, the content of which is hereby incorporated by reference in its entirety.

[0002] Description of Research Funded by the Federal Government Not applicable.

[0003] The present invention generally relates to the field of methods for forming covalently - bonded monomers and graphene - oxide structures on an industrial scale.

Background Art

[0004] Without limiting the scope of the present invention, its background is described in relation to composite materials.

[0005] Graphite is generally used to enhance the mechanical properties, electrical and thermal conductivities of composite materials. Graphite has been used as a component of a number of composite materials, including resins, epoxies, and polymers. Composite materials can be prepared using various reinforcing fillers such as natural graphite, synthetic graphite, carbon black, or carbon fibers together with phenolic resins as the polymer matrix precursors in their liquid and powder forms. However, there is a lack of research on the physical mixing / blending of monomers with sufficient energy not only to exfoliate and disperse graphene oxide (GO) in the monomers but also to cause chemical reactions with the functional groups of graphene oxide.

[0006] Mixing of solids is common and an established method for blending powders in industries that handle solids. For decades, solid-solid mixing has been used for blending powders to homogenize bulk materials and has been designed to handle materials with various bulk solid properties. Based on the practical experience obtained with these various machines, reliable equipment has been built and engineering knowledge for scaling up and predicting mixing behavior has evolved. Today, the same mixing technology is being used for more applications such as improving product quality, coating particles, wet dispersion into molten materials, liquids, deagglomeration, and changing material properties. Now solid-solid mixing is used to achieve classical chemical reactions / processes without the need for solvents. This general technique is called mechanochemistry.

[0007] As classical terms, the activation of chemical reactions uses thermochemistry, electrochemistry, and photochemistry with energy sources. Traditional chemical processes also often utilize catalysts to facilitate covalent bond reactions. These traditional energy sources are reflected in standard physical chemistry textbooks. An alternative route to chemical activation is mechanochemistry. In mechanochemistry, collision energy and catalysts to facilitate covalent bond reactions are used to activate the desired chemical reaction. Some covalent bond reactions can occur without a catalyst, but the conversion efficiency can be very low. However, in practice, the energy generated by mechanochemistry can replace the heat, electricity, photons, or chemical energy directly imparted to the material at the interaction / collision sites between media. An example of a mechanochemical process was demonstrated by Dr. Swager et al.; Dr. Swager used a ball mill and mechanochemical energy and a catalyst to polymerize two white powders, namely, a monomer (1,4-bis(chloromethyl)-2-((2-ethylhexyl)oxy)-5-methoxybenzene), and a strong base (potassium tert-butoxide), to form a red conductive polymer (ACS Macro Lett. 2014, DOI: 10.1021 / mz500098r: (Polyurea Development Association Conference October 4 - 6, 2017 - John Becker Presentation)). They reported that this process was rapid, solvent-free, and produced a more consistent chain length than wet chemical synthesis. The only drawback of this process was that the conversion yield was 60% and the average particle size was less than 5 nm. In addition to the advantages of mixing solids, the physical properties of the GO loading material were significantly improved by the covalent bond reaction between the monomer and the functional groups of GO before the polymer was formed. The covalent bond reaction can easily occur between the COOH and OH functional groups of GO and amine-based monomers.The improvement of physical properties by the covalent bonding reaction can be easily seen from the results published in (PDA Conference - Becker Presentation) Polyurea Development Association Conference October 4 - 6, 2017. According to this publication, it was reported that the GO / polyurea composite with an addition amount of 2% achieved an increase of more than 350% in surface toughness; an increase of more than 50% in elongation at break; and an improvement of more than 290% in tensile strength. The increase in both tensile strength and elongation at break indicates a covalent bonding / chemisorption reaction. As a result of the physical adsorption / non-covalent bonding reaction with a good dispersant, the elongation at break decreases and the tensile strength increases.

[0008] Despite these advantages, there is a need for a consistent industrial-scale process to form covalent monomers and the GO structure.

Prior Art Documents

Non-Patent Documents

[0009]

Non-Patent Document 1

Summary of the Invention

[0010] The present invention relates to a method for producing a chemisorbed graphene oxide polymer composite, comprising the steps of: putting a monomer and graphene oxide into a ball mill; grinding the monomer together with a carbon additive to produce a physically adsorbed monomer graphene oxide material; putting the physically adsorbed monomer graphene oxide material into a polymerization chemical reactor to convert the physically adsorbed monomer graphene oxide into a chemisorbed monomer graphene oxide; and reacting the monomer carbon additive with other monomers or prepolymers to polymerize the material to form a chemisorbed carbon polymer composite.

[0011] In one embodiment, the present invention is a method for producing a chemisorbed graphene oxide polymer composite, comprising the steps of: placing a monomer and graphene oxide into a ball mill; grinding the monomer together with a carbon additive to produce a physically adsorbed monomer graphene oxide material; placing the physically adsorbed monomer graphene oxide material into a polymerization chemical reactor, wherein the physically adsorbed monomer graphene oxide is converted into a chemisorbed monomer graphene oxide by heat treatment; and reacting the monomer carbon additive with another monomer or prepolymer to polymerize the material to form a chemisorbed carbon polymer composite. In one aspect, the chemisorbed carbon polymer composite has both improved physical properties and a corresponding increase in elongation at break. In another aspect, the carbon additive is composed of an oxide of graphite, graphene, carbon, carbon nanotubes, carbon black, or carbon nanowires. In another aspect, the monomer is a liquid or solid particle. In another aspect, the monomer is a particle having a particle diameter of more than 1 μm and less than 500 μm. In another aspect, the monomer is a liquid having a viscosity of more than 1 centipoise and less than 10,000 centipoise. In another aspect, the carbon oxide is composed of at least one of a hydroxide, a peroxide, an epoxide, or a carboxylic acid. In another aspect, the carbon oxide is graphene oxide. In another aspect, the graphene oxide has an oxidation level between 1% and 25%. In another aspect, the graphene oxide is graphene oxide flakes. In another aspect, the graphene oxide flakes have an area-to-thickness ratio of less than 100,000 Å. In another aspect, the heat treatment further includes a catalyst. In another aspect, the catalyst is selected from one or more of ammonia, amines, potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, sodium silicate, and transition metal amino compounds, selected from volatile bases, fixed bases, or permanent bases. In another aspect, the heat treatment includes a temperature of 35, 40, 45, 45, 55, 60, 65, 70, 75, or 75 °C.

[0012] In another embodiment, the present invention is a method of making a chemisorbed graphene oxide polymer composite, the method comprising the steps of: placing a monomer and graphene oxide flakes into a ball mill; grinding the monomer together with a carbon additive to produce a physically adsorbed monomer graphene oxide material; placing the physically adsorbed monomer graphene oxide material into a polymerization chemical reactor, the step of converting the physically adsorbed monomer graphene oxide into a chemisorbed monomer graphene oxide by heat treatment; and reacting the monomer carbon additive with another monomer or prepolymer to polymerize the material to form a chemisorbed carbon polymer composite. In one aspect, the chemisorbed carbon polymer composite has both improved physical properties and a corresponding increase in elongation at break. In another aspect, the carbon additive is composed of oxides of graphite, graphene, carbon, carbon nanotubes, carbon black or carbon nanowires. In another aspect, the monomer is a liquid or solid particle. In another aspect, the monomer is a particle having a particle diameter of more than 1 μm and less than 500 μm. In another aspect, the monomer is a liquid having a viscosity of more than 1 centipoise and less than 10,000 centipoise. In another aspect, the carbon oxide is composed of at least one of hydroxide, peroxide, epoxide or carboxylic acid. In another aspect, the graphene oxide flakes have an oxidation level between 1% and 25%. In another aspect, the graphene oxide flakes have an area-to-thickness ratio of less than 100,000 Å. In another aspect, the reactor further comprises a catalyst. In another aspect, the catalyst is selected from one or more of ammonia, amine, potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, sodium silicate and transition metal amino compounds, selected from volatile bases, non-volatile bases or permanent bases. In another aspect, the heat treatment includes a temperature of 35, 40, 45, 45, 55, 60, 65, 70, 75 or 75 °C.

[0013] In one embodiment, the present invention also includes the steps of putting monomers and graphene oxide into a ball mill; grinding the monomers together with a carbon additive to produce a physically adsorbed monomer graphene oxide material; putting the physically adsorbed monomer graphene oxide material into a polymerization chemical reactor, the step of converting the physically adsorbed monomer graphene oxide into a chemically adsorbed monomer graphene oxide by heat treatment and optionally a catalyst; and reacting the monomer carbon additive with other monomers or prepolymers to polymerize the material to form a chemically adsorbed graphene oxide polymer composite. The chemically adsorbed graphene oxide polymer composite is produced by a method including these steps.

[0014] In one embodiment, the present invention also provides a method for producing chemisorbed graphene oxide, comprising the steps of: placing a monomer and graphene oxide in a ball mill; grinding the monomer together with a carbon additive to produce a physically adsorbed monomer graphene oxide material; and converting the physically adsorbed monomer graphene oxide material into chemisorbed monomer graphene oxide by heat treatment. In one aspect, the carbon additive is composed of an oxide of graphite, graphene, carbon, carbon nanotubes, carbon black, or carbon nanowires. In another aspect, the monomer is a liquid or solid particle. In another aspect, the monomer is a particle having a particle diameter greater than 1 μm and less than 500 μm. In another aspect, the monomer is a liquid having a viscosity greater than 1 centipoise and less than 10,000 centipoises. In another aspect, the graphene oxide has an oxidation level between 1% and 25%. In another aspect, the graphene oxide is graphene oxide flakes. In another aspect, the graphene oxide flakes have an area-to-thickness ratio of less than 100,000 Å. In another aspect, the heat treatment further includes a catalyst. In another aspect, the catalyst is selected from one or more of ammonia, amines, potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, sodium silicate, and volatile bases, non-volatile bases, or permanent bases selected from transition metal amino compounds. In another aspect, the heat treatment includes a temperature of 35, 40, 45, 45, 55, 60, 65, 70, 75, or 75 °C.

Embodiments for Carrying Out the Invention

[0015] The fabrication and use of various embodiments of the present invention will be discussed in detail below, but it should be recognized that the present invention provides many applicable inventive concepts that can be implemented in a wide variety of specific contexts. The specific embodiments discussed herein are merely examples of specific methods for making and using the present invention and do not limit the scope of the present invention.

[0016] To facilitate understanding of the present invention, several terms are defined below. The terms defined herein have the meanings as commonly understood by those skilled in the art related to the present invention. Terms such as "a", "an", and "the" are not intended to refer only to singular entities, but include general classes for which specific examples may be used for illustration. The terms herein are used to describe specific embodiments of the present invention, but their use does not limit the present invention except as outlined in the claims.

[0017] Micron-scale graphene is hundreds of times stronger than steel, harder than diamond, and conducts heat and electricity better than copper. There are challenges in turning these properties into industrially relevant opportunities. The inventors have changed the micron scale to the macro scale by reacting those GO with monomers that create covalent bonds between GO and the polymer in a reactor used for in situ polymerization. When using GO additives, the covalent bond / chemisorption reaction is a way to fundamentally improve the physical properties of the host. The challenges have three elements: 1) reacting the functional groups of GO with monomers of further polymers; 2) inducing sufficient functional groups on GO to enable a desired controlled reaction by reacting with several monomers, resulting in enhancement of the physical properties of the final polymer; and 3) creating a uniform dispersion of functionalized graphene oxide (fGO) or graphene oxide (GO) into the monomer mixture prior to polymerization. The method of the present invention overcomes each of these three challenges.

[0018] The inventors have shown that under appropriate conditions, monomers can be made to react with the functional groups of GO by mixing solids together or by mechanochemical treatment, which requires the following: 1) an oxidation level of GO flakes between 1% and 25% to obtain a covalent bond reaction with monomers, which means a controllable polymerization reaction. At an oxidation level of less than 1%, there is not a sufficient level of functional groups to effectively react with the monomers. Functional groups with an oxidation level of more than 25% will completely react with the monomers and prevent further reactions to form polymers; 2) an area-to-thickness ratio of flakes of less than 100,000 Å; 3) ball milling with a medium of density less than 9 g / cm 3 This ball milling process protects the GO from self-aggregation or coagulation due to van der Waals forces / attraction. The monomers can be liquids, solids or suspensions.

[0019] As used herein, the term "carbon additive" refers to carbon-based monomers or polymers, which include, for example, oxides of graphite, graphene, carbon, carbon nanotubes, carbon black or carbon nanowires. These are typically in powder or particulate form, but may also be suspensions in liquids.

[0020] Non-limiting examples of monomers for use in the present invention include the following polymers, for example, vinylacetic acid (VAA), poly(vinylpyrrolidone), polyethylene oxide (PEO), hydroxypropyl methyl cellulose (HPMC), poly(phenylene oxide) (PPO), dextran, polysaccharide, polyacrylic acid, polymethacrylic acid, polyacrylamide, PEO / PPO, albumin, chitosan, peptide, papain, collagen, a copolymer of lactide and glycolide, a copolymer containing polyacrylic acid, a copolymer containing polymethacrylic acid, a copolymer of any of these homopolymers, a copolymer of these homopolymers by addition of other homopolymers and copolymers, and those forming one or more of plastics such as polystyrene, polypropylene, and polyterephthalate. In other embodiments, the polymer can be a bioabsorbable or biodegradable synthetic polymer, for example, a polyanhydride, a polyorthoester, or a polyhydroxy acid, for example, polylactic acid, polyglycolic acid, and their copolymers or blends. Non-degradable materials can also be used. Examples of suitable materials include ethylene vinyl acetate, derivatives of polyvinyl alcohol, Teflon, nylon, polymethacrylate, and silicone polymers. Other non-degradable materials are ethylene vinyl acetate mesh and polyvinyl alcohol polymer.

[0021] The monomer solid needs to be in powder form, and the diameter of the powder is greater than 0.01 micron and less than 500 microns. For GO with an average diameter of 0.5 μm and a powder having a diameter of less than 1 micron used, the powder coats the GO flakes and reacts with the oxides of the GO flakes. In the case of larger monomer powders, the GO powder coats the monomer / prepolymer powder. Ideally, the monomer powder is 0.01 μm and 1 centipoise. In the case of liquid monomers or suspended monomers, the viscosity needs to be between 1 centipoise and 10,000 centipoise. Ideally, the liquid or suspended monomer is between 1 and 100 centipoise. These parameters enable a covalent bond reaction and are necessary to prevent damage to the monomer or a decrease in the size of GO; 4) a grinding speed of less than 700 rpm and a grinding time of less than 2 hours with the monomer. The shortest time is necessary to enable the covalent bond reaction, while the longest time prevents overheating and decomposition or alteration of the monomer. 5) The process produces a physically adsorbed monomer GO material. The physically adsorbed monomer acts as a compatible solvent, prevents aggregation / coagulation, and enables simple dispersion in the reactor; and 6) when placed in a reactor and treated with other monomers or prepolymers (e.g., polyethylene terephthalate (PET) prepolymer) and / or a catalyst such as sodium hydroxide, the physically adsorbed monomer becomes a chemically adsorbed monomer GO material and can further react to form a polymer structure. The present invention can be implemented with any powder monomer or prepolymer.

[0022] The method of the present invention enables the dispersion and reaction of graphene oxide and the monomer, and a covalent bond between GO and the polymer is formed. The particles of one material (monomer) are coated with the material of another component having OH or COOH functional groups using a grinding process. The inventors used 20 wt% GO to 80 wt% monomer, which is mixed with 300 lbs of media in a 25 gal volume ball milling container. The media used is 9 g / cm 3It has an ultra-high density and a diameter d (d = 10 mm). Crushing or mixing can be carried out in a closed chamber at 100 RPM or less for 5 to 100 minutes to produce a physically adsorbed monomer GO material. When the physically adsorbed monomer GO structure is dispersed in a chemical reactor together with additional monomers, catalysts and / or additional energy, it produces a chemically adsorbed monomer GO material, which is then polymerized into a composite material by in-situ polymerization. The reactor is typically maintained at 65 °C to melt and blend two monomers. However, the reactor can operate at 35, 40, 45, 45, 55, 60, 65, 70, 75 or 75 °C depending on the melting points of one or more than two monomers. The blending is typically carried out at 25 rpm. To facilitate the formation of the polymer, in the method, a catalyst, for example, a volatile base, a non-volatile base or a permanent base selected from one or more of ammonia, amines, potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, sodium silicate and transition metal amino compounds can be used. The resulting composite material shows a significant enhancement (more than 100%) of physical properties, which occurs along with an increase in elongation at break. By controlling the ratio of the components, low density, high electrical conductivity and surface hardness can be achieved.

[0023] The present invention relates to a method for producing a chemically adsorbed graphene oxide polymer composite, comprising the steps of putting a monomer and graphene oxide into a ball mill; crushing the monomer together with a carbon additive to produce a physically adsorbed monomer graphene oxide material; putting the physically adsorbed monomer graphene oxide material into a polymerization chemical reactor, the step of converting the physically adsorbed monomer graphene oxide into a chemically adsorbed monomer graphene oxide; and reacting the monomer carbon additive with other monomers or prepolymers to polymerize the material to form a chemically adsorbed carbon polymer composite, consisting essentially of or consisting of these steps.

[0024] In one embodiment, the present invention is a method for producing a chemisorbed graphene oxide polymer composite, comprising the steps of: putting a monomer and graphene oxide into a ball mill; grinding the monomer together with a carbon additive to produce a physically adsorbed monomer graphene oxide material; putting the physically adsorbed monomer graphene oxide material into a polymerization chemical reactor, the step of converting the physically adsorbed monomer graphene oxide into a chemisorbed monomer graphene oxide by heat treatment; and reacting the monomer carbon additive with other monomers or prepolymers to polymerize the material to form a chemisorbed carbon polymer composite, consisting essentially of or consisting of those steps. In one aspect, the chemisorbed carbon polymer composite has both improved physical properties and a corresponding increase in elongation at break. In another aspect, the carbon additive is composed of oxides of graphite, graphene, carbon, carbon nanotubes, carbon black or carbon nanowires. In another aspect, the monomer is a liquid or solid particle. In another aspect, the monomer is a particle with a particle size greater than 1 μm and less than 500 μm. In another aspect, the monomer is a liquid with a viscosity greater than 1 centipoise and less than 10,000 centipoise. In another aspect, the carbon oxide is composed of at least one of hydroxide, peroxide, epoxide or carboxylic acid. In another aspect, the carbon oxide is graphene oxide. In another aspect, the graphene oxide has an oxidation level between 1% and 25%. In another aspect, the graphene oxide is graphene oxide flakes. In another aspect, the graphene oxide flakes have an area-to-thickness ratio of less than 100,000 Å. In another aspect, the heat treatment further includes a catalyst. In another aspect, the catalyst is selected from one or more of ammonia, amine, potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, sodium silicate and transition metal amino compounds, selected from volatile bases, non-volatile bases or permanent bases. In another aspect, the heat treatment includes a temperature of 35, 40, 45, 45, 55, 60, 65, 70, 75 or 75 °C.

[0025] In another embodiment, the present invention is a method of making a chemisorbed graphene oxide polymer composite, the method comprising the steps of: placing a monomer and graphene oxide flakes into a ball mill; grinding the monomer together with a carbon additive to produce a physically adsorbed monomer graphene oxide material; placing the physically adsorbed monomer graphene oxide material into a polymerization chemical reactor, the step of converting the physically adsorbed monomer graphene oxide into a chemisorbed monomer graphene oxide by heat treatment; and reacting the monomer carbon additive with another monomer or prepolymer to polymerize the material to form a chemisorbed carbon polymer composite, consisting essentially of or consisting of those steps. In one aspect, the chemisorbed carbon polymer composite has both improved physical properties and a corresponding increase in elongation at break. In another aspect, the carbon additive is composed of oxides of graphite, graphene, carbon, carbon nanotubes, carbon black or carbon nanowires. In another aspect, the monomer is a liquid or solid particle. In another aspect, the monomer is a particle having a particle size greater than 1 μm and less than 500 μm. In another aspect, the monomer is a liquid having a viscosity greater than 1 centipoise and less than 10,000 centipoise. In another aspect, the carbon oxide is composed of at least one of hydroxide, peroxide, epoxide or carboxylic acid. In another aspect, the graphene oxide flakes have an oxidation level between 1% and 25%. In another aspect, the graphene oxide flakes have an area-to-thickness ratio of less than 100,000 Å. In another aspect, the reactor further comprises a catalyst. In another aspect, the catalyst is selected from one or more of ammonia, amine, potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, sodium silicate and transition metal amino compounds, selected from volatile bases, non-volatile bases or permanent bases. In another aspect, the heat treatment includes a temperature of 35, 40, 45, 45, 55, 60, 65, 70, 75 or 75 °C.

[0026] In one embodiment, the present invention also includes the steps of placing a monomer and graphene oxide in a ball mill; grinding the monomer with a carbon additive to produce a physically adsorbed monomer graphene oxide material; placing the physically adsorbed monomer graphene oxide material in a polymerization chemical reactor, the step of converting the physically adsorbed monomer graphene oxide to a chemically adsorbed monomer graphene oxide by heat treatment and optionally a catalyst; and reacting the monomer carbon additive with other monomers or prepolymers to polymerize the material to form a chemically adsorbed graphene oxide polymer composite, a chemically adsorbed graphene oxide polymer composite produced by a method consisting essentially of or consisting of these steps.

[0027] In one embodiment, the present invention also includes a method for producing chemisorbed graphene oxide, which includes the steps of putting a monomer and graphene oxide into a ball mill; grinding the monomer together with a carbon additive to produce a physically adsorbed monomer graphene oxide material; and converting the physically adsorbed monomer graphene oxide material into chemisorbed monomer graphene oxide by heat treatment. In one aspect, the carbon additive is composed of oxides of graphite, graphene, carbon, carbon nanotubes, carbon black, or carbon nanowires. In another aspect, the monomer is a liquid or solid particle. In another aspect, the monomer is a particle with a particle size greater than 1 μm and less than 500 μm. In another aspect, the monomer is a liquid with a viscosity greater than 1 centipoise and less than 10,000 centipoises. In another aspect, the graphene oxide has an oxidation level between 1% and 25%. In another aspect, the graphene oxide is graphene oxide flakes. In another aspect, the graphene oxide flakes have an area-to-thickness ratio of less than 100,000 Å. In another aspect, the heat treatment further includes a catalyst. In another aspect, the catalyst is selected from one or more of volatile bases, non-volatile bases, or permanent bases selected from ammonia, amines, potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, sodium silicate, and transition metal amino compounds. In another aspect, the heat treatment includes a temperature of 35, 40, 45, 45, 55, 60, 65, 70, 75, or 75 °C.

[0028] While the present invention and its advantages have been described in detail, it is to be understood that various changes, substitutions, and alternatives can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Further, the scope of this application is not intended to be limited to the specific embodiments of the processes, machines, manufactures, compositions of matter, means, methods, and steps described herein. As will be readily recognized by those skilled in the art, from the disclosure of the present invention, presently existing or later developed processes, machines, manufactures, compositions of matter, means, methods, or steps that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized in accordance with the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufactures, compositions of matter, means, methods, or steps.

[0029] Any embodiment discussed herein can be practiced with respect to any method, kit, reagent, or composition of the invention, and vice versa is contemplated. Further, the compositions of the present invention can be used to achieve the methods of the present invention.

[0030] The specific embodiments described herein are shown by way of example and are not intended to limit the invention. The basic features of the invention can be used in various embodiments without departing from the scope of the invention. Those skilled in the art can recognize or confirm numerous equivalents to the specific procedures described herein using only routine experimentation. Such equivalents are considered to be within the scope of the invention and are encompassed by the claims.

[0031] All publications and patent applications mentioned herein are indicative of the level of skill of those skilled in the art to which the invention pertains. All publications and patent applications are hereby incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference.

[0032] The use of the word "a" or "an" may mean "one" when used in connection with the term "comprising" in the claims and / or the specification, but it also conforms to the meanings of "one or more than two", "at least one", and "one or more than one". Despite the fact that the present disclosure supports only alternative and "and / or" definitions, the use of the term "or" in the claims is used to mean "and / or" unless it is explicitly indicated that it refers only to alternatives or the options are mutually exclusive. Throughout this application, the term "about" is used to indicate that a value includes the error variations inherent in the device, method used to determine the value, or the variations that exist between the subjects of study.

[0033] As used in this specification and the claims, the terms "comprising" (and any form of including such as "comprise" and "comprises"), "having" (and any form of having such as "have" and "has"), "including" (and any form of including such as "includes" and "include"), or "containing" (and any form of containing such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. In embodiments of any of the compositions and methods provided herein, "comprising" may be replaced with "consisting essentially of" or "consisting of". As used herein, the phrase "consisting essentially of" requires the presence of the specified integers or steps and those that do not physically affect the characteristics or functions claimed herein. As used herein, the term "consisting of" is used to indicate the presence of only the recited integers (e.g., features, elements, characteristics, properties, method / process steps or limitations) or groups of integers (e.g., features, elements, characteristics, properties, method / process steps or limitations).

[0034] As used herein, the term "or combinations thereof" refers to all orders and combinations of the recited items preceding the term. For example, "A, B, C, or combinations thereof" is intended to include A, B, C, AB, AC, BC, or ABC, and, where order is important in a particular context, also at least one of BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, combinations containing repeats of one or more items or terms, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, etc. are clearly included. One of ordinary skill in the art will understand that, typically, there is no limit to the number of items or terms in any combination, unless it is clear from the context otherwise.

[0035] As used herein, the approximating language, such as "about", "substantially" or "substantially the same", without limitation, when so modified, is not necessarily absolute or complete and is understood to refer to conditions that are close enough such that one of ordinary skill in the art would assure that such conditions exist. The degree to which the description can vary depends on how large of a change can occur and still one of ordinary skill in the art can recognize that the modified feature still has the required characteristics and the possibility of the unmodified features. Generally, but subject to the foregoing discussion, numerical values in this specification that are modified by approximating language, such as "about", can vary by at least ±1, 2, 3, 4, 5, 6, 7, 10, 12 or 15% from the stated value.

[0036] All compositions and / or methods disclosed and claimed herein can be made and carried out without undue experimentation in light of the present disclosure. While the compositions and methods of the invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and / or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention as defined by the appended claims.

[0037] For the benefit of the Patent Office and any readers of any patent cited in this application in interpreting the appended claims, Applicant wishes to note that no claim of this application is intended to implement 35 U.S.C. § 112, paragraph 6, 35 U.S.C. § 112, paragraph (f), or the equivalent, as being for a means or step for performing a function unless the term "means for" or "step for" is expressly recited in a particular claim.

[0038] For each claim, each dependent claim can depend on both the independent claim and each of the preceding dependent claims of all claims, provided that the preceding claim provides a proper antecedent basis for the claim terms or elements.

[0039] (References) 1. ACS Macro Lett. 2014, DOI: 10.1021 / mz500098r: (Polyurea Development Association Conference October 4 - 6, 2017 - John Becker Presentation)

Claims

1. A method for producing a chemisorbed graphene oxide polymer composite, comprising: placing a monomer and graphene oxide in a ball mill, wherein the graphene oxide is graphene oxide flakes having an area-to-thickness ratio of less than 100,000 Å; grinding the monomer together with the graphene oxide to produce a physically adsorbed monomer graphene oxide material; placing the physically adsorbed monomer graphene oxide material in a polymerization chemical reactor, converting the physically adsorbed monomer graphene oxide into a chemisorbed monomer graphene oxide by heat treatment, wherein the heat treatment comprises a catalyst selected from one or more of ammonia, potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, and sodium silicate, which are selected from volatile bases or non-volatile bases; and reacting the chemisorbed monomer graphene oxide with another monomer or prepolymer to polymerize the material to form a chemisorbed graphene oxide polymer composite The method as described above.

2. The method according to claim 1, wherein the graphene oxide has an oxidation level between 1% and 25% by weight.

3. The method according to claim 1, wherein the monomer is particles having a particle diameter of more than 1 μm and less than 500 μm, or a liquid having a viscosity of more than 1 centipoise and less than 10,000 centipoise.

4. A method for producing a chemisorbed monomer graphene oxide, comprising: placing a monomer and graphene oxide in a ball mill, wherein the graphene oxide is graphene oxide flakes having an area-to-thickness ratio of less than 100,000 Å; grinding the monomer together with the graphene oxide to produce a physically adsorbed monomer graphene oxide material; converting the physically adsorbed monomer graphene oxide material into a chemisorbed monomer graphene oxide by heat treatment, wherein the heat treatment comprises a catalyst selected from one or more of ammonia, potassium hydroxide, lithium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, and sodium silicate, which are selected from volatile bases or non-volatile bases The method as described above.

5. The method according to claim 4, wherein the monomer is a liquid or solid particle.

6. The method according to claim 4, wherein the monomer is a particle having a particle diameter of more than 1 μm and less than 500 μm, or is a liquid having a viscosity of more than 1 centipoise and less than 10,000 centipoises.

7. The method according to claim 4, wherein the graphene oxide has an oxidation level between 1% and 25% by weight.