TW201938660A - Products containing graphene-mediated metallized polymer component - Google Patents

Abstract

Provided is a surface-metalized polymer article comprising a polymer component having a surface, a first layer of combined multiple graphene sheets and an optional conductive filler coated on the polymer component surface, and a second layer of a plated metal deposited on the first layer, wherein the multiple graphene sheets contain single-layer or few-layer graphene, and wherein the multiple graphene sheets and conductive filler are bonded to the polymer component surface with or without an adhesive resin. In certain embodiments, this article is selected from a vehicle component, an electronic appliance, an electronic device, a food packaging film or bag, a protective clothing, an antistatic film or bag, a susceptor in microwave cooking, a blanket, an anti-reflection accessary, a toy, a product label, a mailer, a sports card, a greeting card, a solar control window film, or a stamping foil.

Description

Products including graphene-mediated metallized polymer parts

This application claims priority from US Patent Application No. 15 / 924,633, filed on March 19, 2018, and US Patent Application No. 15 / 943,087, filed on April 2, 2018, which are hereby incorporated by reference.

This disclosure relates generally to the field of metallization of polymer component surfaces, and more particularly to graphene-mediated metallized polymer articles and processes and equipment needed to produce them.

Metallized plastics are often used for decorative purposes. For example, metallize the surface of plastics such as acrylonitrile-butadiene-styrene (ABS) and ABS-polycarbonate blends for use in bathroom accessories, automotive accessories, furniture, hardware, jewelry and buttons / knobs . These manufactured articles can be metalized to give the article an attractive appearance.

In addition, plastic, rubber, and polymer matrix composites (such as fiber-reinforced or additive-filled thermoplastic, thermoset, and rubber matrix composites) can also be metalized for functional purposes. For example, metallization of plastic-based electronic components can be performed to shield electromagnetic interference (EMI). In addition, the surface properties of polymer parts can be changed in a controlled manner by metal coating.

Articles made of non-conductive polymers (such as plastic, rubber, polymer matrix composites, etc.) can be metalized by electroless metallization processes. In a typical process, the article is first cleaned and etched, then treated with a precious metal (such as palladium), and finally metalized in a metallizing solution. The etching step typically involves the use of chromic acid or chromosulfuric acid. The etching step is used to make the surface of the article susceptible to subsequent metallization by a corresponding solution in a subsequent processing step with improved surface wettability, and to make the final deposited metal adhere well to the polymer surface.

In the etching step, the surface of the polymer article is etched with chromic sulfuric acid to form surface micro holes, and metal is deposited and adhered to these surface micro holes. After the etching step, the surface of the polymer part is activated by means of an activating agent (or activator) typically containing a precious metal, and then metallized using electroless plating. A thicker metal layer can then be deposited electrolytically.

The etching solution based on chromic acid is toxic and should therefore be replaced if possible. For example, a chromium-sulfuric acid-based etching solution may be replaced with an etching solution containing a permanganate. The use of permanganates in alkaline media for metallization of circuit boards as electronic circuit carriers has long been established. Since the hexavalent state (manganate) produced during oxidation is water-soluble and has sufficient stability under alkaline conditions, similar to trivalent chromium, manganate can be electrolytically oxidized back to the original oxidant, In this case it is permanganate. For the metallization of ABS plastics, alkaline permanganate solutions have been found to be inappropriate, since in this way it is not possible to obtain sufficient adhesion strength between the metal layer and the plastic substrate. This adhesion strength is measured in a "peel test" and should have a value of at least 0.4 N / mm.

As an alternative to chromic acid, WO 2009/023628 A2 proposes the use of a strongly acidic solution containing an alkali metal permanganate. This solution contains about 20 g / l of an alkali metal permanganate in 40-85% by weight of phosphoric acid. Such solutions form colloidal manganese (IV) species that are difficult to remove. In addition, colloids are also difficult to form with high quality coatings. To solve this problem, WO 2009/023628 A2 proposes the use of a manganese (VII) source that does not contain any alkali metal or alkaline earth metal ions. However, the preparation of such manganese (VII) sources is expensive and inconvenient.

Therefore, there is an urgent need for industrial-scale metallization of polymer component surfaces without the use of chromic acid, chromic sulfuric acid, or alkali metal permanganates.

Another major problem with prior art metallization processes is the idea that after the etching step, the surface of the polymer part must be activated by means of an activating agent, which typically contains a precious metal (such as palladium). Noble metals are known to be rare and expensive. In an alternative process [L. Naruskevicius et al. "Process for metallizing a plastic surface" [U.S. Patent No. 6712948 (03/30/2004)], chemically etched plastic The surface is treated with a metal salt solution containing a cobalt salt, a silver salt, a tin salt, or a lead salt. However, activated plastic surfaces must be further treated with a sulfide solution. The entire process is slow, tedious and expensive.

Therefore, there is another urgent need for industrial-scale metallization of polymer component surfaces without the use of expensive precious metals in the activating reagent or, if not all, the activation step.

The present disclosure provides a surface metallized polymer product. The polymer product includes a polymer part having a surface, a first part composed of a plurality of graphene sheets, and a conductive filler as required, which is coated on the surface of the polymer part. One layer, and a second plated metal layer deposited on the first layer, wherein the plurality of graphene sheets comprise a material selected from a primary graphene material having a substantially non-carbon element of 0% or 25% by weight non-carbon element non-primary graphene material single-layer or few-layer graphene sheet, wherein the non-primary graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, and chlorinated graphite Graphene, brominated graphene, graphene iodide, graphene hydrogenated, graphene nitride, doped graphene, chemically functionalized graphene, or a combination thereof, and wherein the plurality of graphene sheets and the conductive filler are present in Or without adhesive resin bonded to the surface of the polymer part, and the first layer has a thickness from 0.34 nm to 30 μm.

With such high-quality metal coatings mediated by graphene sheets, polymer parts (such as plastic, rubber, and polymer composites) can exhibit a beautiful and expensive chrome appearance and exhibit excellent resistance Abrasiveness, barrier properties (such as preventing penetration of water vapor, oxygen, etc.), heat radiation reflection characteristics, corrosion resistance, strength and hardness. As a result, they can be used as design elements in automobiles, bicycles and motorcycles, appliances, electronics, kitchens and bathrooms. For example, in vehicles, radiator grilles, mirror covers, door handles, and trims are items with such finishes. Examples of metallized polymer parts in electronic devices and appliances include hi-fi equipment, buttons and covers for mobile phones and coffee machines, LED lamp covers, EMI shielding coatings for electronic devices, telecommunications equipment (such as smart phones, smart phones, Watches, wearables), metalized cases, laptops, tablets, telescope parts, susceptors (such as microwave popcorn bags) for cooking in a microwave oven.

Surface metallized polymer articles for bathroom or kitchen accessories can be selected from faucets, shower heads, pipes, pipes, connectors, adapters, sinks (such as kitchen or bathroom sinks), bathtub covers, spouts, sink covers, bathrooms Accessories, or kitchen accessories.

Other uses for metallized polymer parts include diffusion barrier coatings in food packaging (such as candy wrappers), antistatic bags, protective clothing (high-energy radiation shields, heat shields for fuel fires, radiation heat reflectors, etc.) ), Aluminized blankets for patient warming, children's toys, product labels, mailer, sports cards, greeting cards, solar control window films, stamped foils, etc.

This disclosure also provides an apparatus that can be used to produce the surface metallized article. The equipment for manufacturing a surface metallized polymer article may include: (a) a graphene deposition chamber (eg, a graphene dispersion bath), the graphene deposition chamber containing a graphene dispersion, the graphene dispersion comprising a A plurality of graphene sheets in a first liquid medium and an optional conductive filler, and an optional binder resin dissolved in the first liquid medium, wherein the graphene deposition chamber is operated to place the graphene sheets and as needed Of conductive filler is deposited on the surface of at least one polymer part to form at least one graphene-coated polymer part; and (b) a metallization chamber (eg, a metal plating bath) in working relationship with the graphene deposition chamber The metallization chamber contains a plating solution for plating a layer of a desired metal on the at least one graphene-coated polymer part to obtain a surface metallized polymer article; wherein the plurality of graphene The sheet comprises a single or few layers selected from a primary graphene material having substantially 0% non-carbon elements or a non-primary graphene material having 0.001 to 25% by weight non-carbon elements Inkene sheet, wherein the non-native graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, graphene chloride, brominated graphene, graphene iodide, hydrogenated graphene, graphite nitride Ene, doped graphene, chemically functionalized graphene, or a combination thereof.

The apparatus may further include a movable carrier for carrying the at least one polymer part and bringing the at least one polymer part into contact with the graphene dispersion (eg, for impregnating the at least one polymer part In the graphene dispersion bath, and then withdrawing the at least one polymer part from the bath) to produce the at least one graphene-coated polymer part and / or polymerize the at least one graphene-coated polymer An object part is in contact with the plating solution (eg, for immersing the at least one graphene-coated polymer part in the plating solution in the metal plating bath, and then the at least one graphene-coated polymer part Exit from the plating bath) to obtain the desired surface metallized polymer article.

The apparatus may further include a drying, heating, or curing providing device in working relationship with the graphene deposition chamber (eg, above the graphene dispersion bath) for partially removing from the at least one graphene-coated polymer part. Or completely removing the first liquid medium and / or for polymerizing or curing the optional binder resin to produce the at least one graphene coating comprising a plurality of graphene sheets bonded to a surface of the at least one polymer part Covered polymer parts.

In the apparatus, the plating solution may include an electroless plating solution, an electrochemical plating solution, or an electrolytic solution. Preferably, the plating solution includes a chemical plating solution containing a metal salt dissolved in water or an organic solvent.

In some embodiments, the conductive filler is selected from the group consisting of metal nanowires, carbon fibers, carbon nanofibers, carbon-coated fibers, conductive polymer fibers, SnO ₂ , ZnO ₂ , In ₂ O _3, or indium tin oxide ( ITO) nanofibers or nanowires, conductive polymers not in the form of fibers, or a combination thereof. The metal nanowire is preferably selected from silver (Ag), gold (Au), copper (Cu), platinum (Pt), zinc (Zn), cadmium (Cd), cobalt (Co), molybdenum (Mo), Nanowires of aluminum (Al), or a combination thereof. The conductive polymer is preferably selected from the group consisting of polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothioindene (PITN) ), Polyheteroarylene (PArV) (wherein the heteroarylene group may be thiophene, furan or pyrrole), polyparaphenylene (PpP), polyphthalocyanine (PPhc), and the like, and their Derivatives, and combinations thereof.

In some embodiments, the chemical functional group is selected from an alkyl or aryl silane, an alkyl or aralkyl group, a hydroxyl group, a carboxyl group, an amine group, a sulfonate group (--SO ₃ H), an aldehydic group, a quinoidal, a fluorocarbon, or a combination thereof.

Alternatively, the functional group includes a derivative of an azide compound selected from the group consisting of 2-azidoethanol, 3-azidopropan-1-amine, 4- (2- Azidoethoxy) -4-oxobutanoic acid, 2-azidoethyl-2-bromo-2-methylpropanoate, chloroformate, azidocarbonate, Dichlorocarbene, carbene, aryne, azene, (R-)-oxycarbonylazene, where R = any of the following groups:

And combinations.

In certain embodiments, the functional group is selected from the group consisting of a hydroxyl group, a peroxide, an ether, a keto group, and an aldehyde. In certain embodiments, the functionalizing agent contains a functional group selected from the group consisting of: SO ₃ H, COOH, NH ₂ , OH, R'CHOH, CHO, CN, COCl, halogen Root (halide), COSH, SH, COOR ', SR', SiR ' ₃ , Si (-OR'-) _y R ' _3-y , Si (-O--SiR' _2- ) OR ' , R ", Li, AlR ' ₂ , Hg--X, TlZ ₂ and Mg--X; where y is an integer equal to or less than 3, and R' is hydrogen, alkyl, aryl, cycloalkyl, or arane Group, cycloaryl group or poly (alkyl ether), R "is a fluoroalkyl group, a fluoroaryl group, a fluorocycloalkyl group, a fluoroaralkyl group or a cycloaryl group, X is a halogen group, and Z is a Carboxylate or trifluoroacetate, and combinations thereof.

The functional group may be selected from the group consisting of amidoamine, polyamine, aliphatic amine, modified aliphatic amine, cycloaliphatic amine, aromatic amine, acid anhydride, ketimine, and diethyl ether Triamine (DETA), Triethylenetetraamine (TETA), Tetraethyleneethylpentamine (TEPA), Polyethylenepolyamine, Polyamine epoxy adduct, Phenol hardener, Non-brominated curing agent , Non-amine curing agents, and combinations thereof.

In some embodiments, the functional group may be selected from: OY, NHY, O = C--OY, P = C--NR'Y, O = C--SY, O = C--Y, --CR ' 1--OY, N'Y or C'Y, and Y is a protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or enzyme substrate Functional group of the transition state analogue or selected from R '-OH, R'-NR ' ₂ , R'SH, R'CHO, R'CN, R'X, R'N ⁺ (R') _{3 ^{X -, R'SiR '3, R'Si}} (- OR' -) y R '3-y, R'Si (- O - SiR' 2 -) OR ', R' - R ", R '-N--CO, (C ₂ H ₄ O--) _w H, (--C ₃ H ₆ O--) _w H, (--C ₂ H ₄ O) _w --R ', (C ₃ H ₆ O) _w --R', R ', and w is an integer greater than 1 and less than 200.

Surface metallized polymer articles may be selected from faucets, shower heads, pipes, pipes, connectors, adapters, sinks (such as kitchen or bathroom sinks), bathtub covers, spouts, sink covers, bathroom accessories, or kitchen accessories.

In some embodiments, the first layer contains a binder resin that chemically bonds the graphene sheet and the conductive filler to the surface of the polymer component. In certain alternative embodiments, the graphene sheet comprises a non-native graphene material having a non-carbon element content from 0.01% to 20% by weight, and these non-carbon elements include a member selected from the group consisting of oxygen, fluorine, chlorine, bromine, An element of iodine, nitrogen, hydrogen, or boron. These graphene sheets can be further chemically functionalized.

The polymer component may include plastic, rubber, thermoplastic elastomer, polymer matrix composite, rubber matrix composite, or a combination thereof. In certain embodiments, the polymer component comprises a thermoplastic, a thermosetting resin, an interpenetrating network, a rubber, a thermoplastic elastomer, a natural polymer, or a combination thereof. In certain preferred embodiments, the polymer component comprises a plastic selected from the group consisting of acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polycarbonate Ester, polyamide or nylon, polystyrene, high impact polystyrene (HIPS), polyacrylate, polyethylene, polypropylene, polyacetal, polyester, polyether, polyetherfluorene, polyetheretherketone , Polyfluorene, polyphenylene ether (PPO), polyvinyl chloride (PVC), polyimide, polyimide, imine, polyurethane, polyurea, or a combination thereof.

In the surface metallized polymer article, the metal to be plated is preferably selected from the group consisting of copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, alloys thereof, or combinations thereof. There are no restrictions on the type of metal that can be plated.

The graphene sheet can be further modified with nano-sized particles or coatings (having a diameter or thickness from 0.5 nm to 100 nm) of a catalytic metal selected from cobalt, nickel, copper, iron, manganese, tin, zinc , Lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof, and wherein the catalytic metal is different in chemical composition from the metal to be plated.

In some embodiments, the surface of the polymer component contains only small openings or holes having a diameter or depth of <0.1 μm before the first layer on which the graphene sheet and conductive filler are deposited.

In some embodiments, a plurality of graphene sheets and an adhesive resin for conductive fillers are bonded to the surface of a polymer part, having a thickness of from 1/5000 to 1/10, preferably from 1/1000 to 1/100. Weight ratio of binder to graphene.

This disclosure also provides a method for producing a surface metallized polymer article, the method comprising: (a) providing a graphene / conductive filler mixture dispersion, the dispersion comprising a plurality of graphene flakes dispersed in a liquid medium and A conductive filler that brings the surface of the polymer part into contact with the dispersion and promotes the deposition of the graphene sheets and the conductive filler onto the surface of the surface-treated polymer part, wherein the graphene sheets and the conductive filler are bonded to the surface To form a bonded graphene sheet and conductive filler layer covering the surface of the polymer component (ie, to form a graphene / conductive filler-covered polymer component surface); and (b) chemically, A metal layer is deposited physically, electrochemically or electrolytically to form the surface metallized polymer article.

In some embodiments, the method further includes the step of subjecting the surface of the polymer component to a grinding process, an etching process, or a combination thereof before step (a). In some embodiments, step (a) includes the step of subjecting the surface of the polymer component to an etching treatment using an etchant selected from an acid, an oxidant, a metal salt, or a combination thereof.

Preferably, the method further includes a step of subjecting the surface of the polymer member to an etching treatment without using chromic acid or chromic sulfuric acid before step (a). More preferably, the method further comprises subjecting the surface of the polymer member to an etching treatment using an etchant selected from an acid, an oxidizing agent, a metal salt, or a combination thereof under a mild etching condition before step (a). A step in which the etching is performed at a sufficiently low temperature for a short period of time so as not to generate micro holes having an average size greater than 0.1 μm.

The graphene sheet can be further modified with nano-sized particles or coatings of a catalytic metal having a diameter or thickness from 0.5 nm to 100 nm, the catalytic metal being selected from the group consisting of cobalt, nickel, copper, iron, manganese, tin, zinc, Lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof.

In certain embodiments, step (a) includes soaking or immersing the polymer part in a dispersion, and then removing the polymer part from the dispersion to achieve deposition of graphene sheets and conductive fillers onto the warped surface On the surface of the treated polymer part, where the graphene sheets and the conductive filler are bonded to the surface to form a layer of the combined graphene sheet and the conductive filler. Alternatively, a graphene / conductive filler mixture dispersion can be simply sprayed onto the surface of the polymer part, allowing the liquid components to evaporate, and allowing the adhesive (if present) to cure or solidify.

In the disclosed method, step (b) may include immersing the polymer part in a metallization bath. In a preferred procedure, step (b) includes immersing a polymer part containing a layer of bonded graphene sheets / conductive fillers in an electroless plating bath containing a metal salt dissolved in a liquid medium and then withdrawing therefrom to achieve The step of metallizing the surface of the polymer part.

In certain embodiments, the graphene / conductive filler mixture dispersion further comprises a binder resin having a binder to graphene weight ratio from 1/5000 to 1/10.

The graphene sheet can be further modified with nano-sized particles or coatings of a catalytic metal having a diameter or thickness from 0.5 nm to 100 nm, the catalytic metal being selected from the group consisting of cobalt, nickel, copper, iron, manganese, tin, zinc, Lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof.

The liquid medium may include permanganic acid, phosphoric acid, nitric acid, or a combination thereof dissolved in the liquid medium. In certain embodiments, the liquid medium contains an acid, an oxidant, a metal salt, or a combination thereof dissolved therein.

Step (b) may include soaking the polymer part in a metallization bath to complete electroless or electroless plating. The high conductivity of the deposited graphene sheet and the conductive filler enables one or more metal layers to be plated on the surface of the graphene / conductive filler-coated polymer part. Alternatively, physical vapor deposition, sputtering, plasma deposition, etc. may be selected to complete the final metallization process.

The present disclosure also provides a graphene / conductive filler mixture dispersion comprising a plurality of graphene flakes and a conductive filler dispersed in a liquid medium, wherein the plurality of graphene flakes comprise A non-carbon elementary graphene material or a single-layer or few-layer graphene sheet having a non-carbon elemental non-carbon elementary non-carbon graphene material, wherein the non-primary graphene is selected from graphene oxide, Reduced graphene oxide, fluorinated graphene, chlorinated graphene, graphene bromide, graphene iodide, hydrogenated graphene, graphitized nitride, doped graphene, chemically functionalized graphene, or a combination thereof, And wherein the dispersion further comprises one or more species selected from: (i) a binder resin dissolved or dispersed in the liquid medium, wherein the weight ratio of the binder to graphene is from 1/5000 to 1 / 10; (ii) an etchant selected from an acid, an oxidant, a metal salt, or a combination thereof; (iii) a nanoscale particle or coating of a catalytic metal having a diameter or thickness from 0.5 nm to 100 nm, the catalytic metal Selected from cobalt and nickel , Copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof; or (iv) a combination thereof.

The conductive filler may be selected from: metal nanowires, carbon fibers, carbon nanofibers, carbon coated fibers, conductive polymer fibers, SnO ₂ , ZnO ₂ , In ₂ O ₃ or indium tin oxide (ITO) nanofibers Or nanowires, conductive polymers not in the form of fibers, or a combination thereof. Metal nanowires can be selected from silver (Ag), gold (Au), copper (Cu), platinum (Pt), zinc (Zn), cadmium (Cd), cobalt (Co), molybdenum (Mo), and aluminum (Al ) Nanowires, or a combination of them. The conductive polymer is preferably selected from the group consisting of polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothioindene (PITN) ), Polyheteroarylene (PArV) (wherein the heteroarylene group may be thiophene, furan or pyrrole), polyparaphenylene (PpP), polyphthalocyanine (PPhc), and the like, and their Derivatives, and combinations thereof.

In the graphene-conductive filler dispersion, nanoscale particles or coatings of catalytic metals may be deposited or modified on the surface of the plurality of graphene sheets. The acid may be selected from the group consisting of permanganic acid, phosphoric acid, nitric acid, chromic acid, chromic sulfuric acid, carboxylic acid, acetic acid, and ascorbic acid, or a combination thereof.

Preferred first chemical functionalities or preferred second chemical functionalities have been discussed earlier in this section.

Definitions of various terms and phrases used throughout this specification are included below.

The term "graphene sheet" means a material that contains one or more planar sheets of bonded carbon atoms that are densely packed in a hexagonal lattice, where the carbon atoms are bonded by strong in-plane covalent bonding Together, and also contains most of the complete ring structure throughout the interior. Preferably, at least 80% of the internal aromatic bonds are intact. In the c-axis (thickness) direction, these graphene planes can be weakly bonded together by Van der Waals force. Graphene sheets can contain non-carbon atoms on their edges or surfaces, such as OH and COOH functional groups. The term graphene sheet includes native graphene, graphene oxide, reduced graphene oxide, halogenated graphene (including fluorinated graphene and chlorinated graphene), nitrided graphene, hydrogenated graphene, doped graphene, functional Graphene, and combinations thereof. Typically, non-carbon elements make up from 0% to 25% by weight of the graphene sheet. Graphene oxide may contain up to 53% by weight of oxygen. The term "doped graphene" encompasses graphene with less than 10% non-carbon elements. The non-carbon element may include hydrogen, oxygen, nitrogen, magnesium, iron, sulfur, fluorine, bromine, iodine, boron, phosphorus, sodium, and combinations thereof. The graphene sheet may include a single layer of graphene or a few layers of graphene, wherein the few layers of graphene are defined as graphene platelets formed by less than 10 graphene planes. The graphene sheet may further include a graphene nanobelt. "Native graphene" encompasses graphene sheets having substantially 0% non-carbon elements. "Nanographene platelet" (NGP) refers to a graphene plate having a thickness from less than 0.34 nm (single layer) to 100 nm (multilayer).

The term "substantially" and its variants are defined to be largely, but not necessarily completely, specified (as understood by those skilled in the art), and in a non-limiting embodiment, generally Refers to the range within 10%, 5%, 1%, or 0.5% of the reference range.

The term "substantially" and its variants are defined to a large extent but not necessarily completely as specified (as understood by those skilled in the art), and in a non-limiting embodiment, generally are Refers to the range within 10%, 5%, 1%, or 0.5% of the reference range.

Other objects, features and advantages of the present invention will become apparent from the following drawings, descriptions and examples. It should be understood, however, that the drawings, descriptions, and examples, although indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. In other embodiments, features from specific embodiments may be combined with features from other embodiments.

The present disclosure provides a surface metallized polymer product. The polymer product includes a polymer part having a surface, a first part composed of a plurality of graphene sheets, and a conductive filler as required, which is coated on the surface of the polymer part. One layer, and a second plated metal layer deposited on the first layer, wherein the plurality of graphene sheets comprise a material selected from a primary graphene material having a substantially non-carbon element of 0% or 25% by weight non-carbon element non-primary graphene material single-layer or few-layer graphene sheet, wherein the non-primary graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, and chlorinated graphite Graphene, brominated graphene, graphene iodide, graphene hydrogenated, graphene nitride, doped graphene, chemically functionalized graphene, or a combination thereof, and wherein the plurality of graphene sheets and the conductive filler are present in Or without a binder resin, as shown in FIG. 2. This first layer has a thickness typically from 0.34 nm to 30 μm (preferably from 1 nm to 1 μm, and further preferably from 1 nm to 100 nm). The second layer (overlay metal layer) preferably has a thickness from 0.5 nm to 1.0 mm, more preferably from 1 nm to 10 μm, and most preferably from 10 nm to 1 μm. This metal-plated polymer article can be easily and easily produced using a surprisingly simple and effective method also described herein. Functionalized graphene sheets are surprisingly capable of bonding to many types of polymer component surfaces without the use of adhesive resins.

In certain embodiments, the surface metallized polymer article is not a bathroom or kitchen accessory, but is selected from vehicle components, electrical appliances, electronic equipment, food packaging films or bags, protective clothing, antistatic films or bags, microwave cooking Sensors, blankets, anti-reflection accessories, children's toys, product labels, express bags, sports cards, greeting cards, solar control window films, or stamped foils. The vehicle component may be selected from a radiator grille, a mirror cover, a door handle, or a trim. The electrical or electronic device may include a button or cover of a high-fidelity audio device, a mobile phone, a coffee machine, an LED lamp cover, a wearable device, an electronic watch, a laptop computer, a tablet computer, or an EMI shielding coating for an electronic device.

This disclosure also provides an apparatus that can be used to produce the surface metallized polymer article. In certain embodiments, as shown in FIG. 3, the apparatus may include: (a) a graphene deposition chamber (eg, a graphene dispersion bath 12), the graphene deposition chamber containing a graphene dispersion 14, the graphite The olefin dispersion includes a plurality of graphene sheets dispersed in a first liquid medium and an optional conductive filler, and an optional binder resin dissolved in the first liquid medium, wherein the graphene deposition chamber is operated to convert these Graphene sheets and optionally conductive fillers are deposited on the surface of at least one polymer part to form at least one graphene-coated polymer part (eg, faucet assembly 10); and (b) with the graphene deposition chamber Metallization chamber in working relationship (eg, metal plating bath 22) (eg, disposed near graphene dispersion bath 12), the metallization chamber containing a plating solution 24 for coating the at least one graphene The polymer part is plated with a layer of the desired metal to obtain the surface metallized polymer article.

Preferably, the graphene deposition chamber 12 has an inlet 16 and an outlet 18. Correspondingly, a fresh graphene dispersion can be pumped into the graphene deposition chamber through the inlet, and a waste graphene dispersion can be pumped out through the outlet. . It is further preferred that the metallization chamber 22 has an inlet 26 and an outlet 28. Correspondingly, fresh plating solution can be pumped into the metallization chamber through the inlet, and waste graphene dispersion can be pumped out through the outlet.

The apparatus may further include a movable carrier for carrying the at least one polymer part and bringing the at least one polymer part into contact with the graphene dispersion (eg, for impregnating the at least one polymer part In the graphene dispersion bath, and then withdrawing the at least one polymer part from the bath) to produce the at least one graphene-coated polymer part and / or polymerize the at least one graphene-coated polymer An object part is in contact with the plating solution (eg, for immersing the at least one graphene-coated polymer part in the plating solution in the metal plating bath, and then the at least one graphene-coated polymer part Exit from the plating bath) to obtain the desired surface metallized polymer article.

The apparatus may further include a drying, heating or curing providing device 32 in working relationship with the graphene deposition chamber (eg, above and between the graphene dispersion bath and the metallization chamber) for coating from the at least one graphene Partially or completely remove the first liquid medium from the polymer part and / or for polymerizing or curing the optional adhesive resin to produce the graphene sheet comprising a plurality of graphene sheets bonded to a surface of the at least one polymer part At least one graphene-coated polymer part. As an example, as shown schematically in FIG. 3, it is shown that the faucet assembly 10 has been withdrawn from the graphene deposition bath 12 and is being heated, dried or cured. After completing the drying / heating / curing process, the faucet is immersed in the metallization bath 22.

In the apparatus, the plating solution 24 may include an electroless plating solution, an electrochemical plating solution, or an electrolytic solution. Preferably, the plating solution includes an electroless plating solution containing a metal salt dissolved in water or an organic solvent (for example, CuSO ₄ or NiNO ₃ dissolved in water for copper or nickel plating). The various graphene sheets incorporated on the surface of a polymer component are unexpectedly capable of attracting metal ions to the surface of a graphene-coated or graphene-coated polymer component. The adhesion of the metal on this surface is surprisingly strong, scratch-resistant and hard. The deposited metal layer provides the desired gloss and metallic appearance on the surface of the polymer part.

The operations of the above procedures can be performed continuously or intermittently and can be fully automated.

In some embodiments, the conductive filler is selected from the group consisting of metal nanowires, carbon fibers, carbon nanofibers, carbon-coated fibers, conductive polymer fibers, SnO ₂ , ZnO ₂ , In ₂ O _3, or indium tin oxide ( ITO) nanofibers or nanowires, conductive polymers not in the form of fibers, or a combination thereof. The metal nanowire is preferably selected from silver (Ag), gold (Au), copper (Cu), platinum (Pt), zinc (Zn), cadmium (Cd), cobalt (Co), molybdenum (Mo), Nanowires of aluminum (Al), or a combination thereof. The conductive polymer is preferably selected from the group consisting of polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothioindene (PITN) ), Polyheteroarylene (PArV) (wherein the heteroarylene group may be thiophene, furan or pyrrole), polyparaphenylene (PpP), polyphthalocyanine (PPhc), and the like, and their Derivatives, and combinations thereof.

In some embodiments, the chemically functionalized graphene sheet contains a chemical functional group selected from the group consisting of an alkyl or aryl silane, an alkyl or aralkyl group, a hydroxyl group, a carboxyl group, an amine group , A sulfonic acid group (--SO ₃ H), an aldehyde group, a quinone group, a fluorocarbon, or a combination thereof. Alternatively, the functional group includes a derivative of an azide compound selected from the group consisting of 2-azidoethanol, 3-azidopropan-1-amine, 4- (2- Azidoethoxy) -4-oxobutanoic acid, 2-azidoethyl-2-bromo-2-methylpropanoate, chloroformate, azidocarbonate, Dichlorocarbene, carbene, aryne, azene, (R-)-oxycarbonylazene, where R = any of the following groups:

And combinations.

In certain embodiments, the functional group is selected from the group consisting of a hydroxyl group, a peroxide, an ether, a keto group, and an aldehyde. In certain embodiments, the functionalizing agent contains a functional group selected from the group consisting of: SO ₃ H, COOH, NH ₂ , OH, R'CHOH, CHO, CN, COCl, halogen Root (halide), COSH, SH, COOR ', SR', SiR ' ₃ , Si (-OR'-) _y R ' _3-y , Si (-O--SiR' _2- ) OR ' , R ", Li, AlR ' ₂ , Hg--X, TlZ ₂ and Mg--X; where y is an integer equal to or less than 3, and R' is hydrogen, alkyl, aryl, cycloalkyl, or arane Group, cycloaryl group or poly (alkyl ether), R "is a fluoroalkyl group, a fluoroaryl group, a fluorocycloalkyl group, a fluoroaralkyl group or a cycloaryl group, X is a halogen group, and Z is a Carboxylate or trifluoroacetate, and combinations thereof.

The functional group may be selected from the group consisting of amidoamine, polyamine, aliphatic amine, modified aliphatic amine, cycloaliphatic amine, aromatic amine, acid anhydride, ketimine, and diethyl ether Triamine (DETA), Triethylenetetraamine (TETA), Tetraethyleneethylpentamine (TEPA), Polyethylenepolyamine, Polyamine epoxy adduct, Phenol hardener, Non-brominated curing agent , Non-amine curing agents, and combinations thereof.

In some embodiments, the functional group may be selected from: OY, NHY, O = C--OY, P = C--NR'Y, O = C--SY, O = C--Y, --CR ' 1--OY, N'Y or C'Y, and Y is a protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or enzyme substrate Functional group of the transition state analogue or selected from R '-OH, R'-NR ' ₂ , R'SH, R'CHO, R'CN, R'X, R'N ⁺ (R') _{3 ^{X -, R'SiR '3, R'Si}} (- OR' -) y R '3-y, R'Si (- O - SiR' 2 -) OR ', R' - R ", R '-N--CO, (C ₂ H ₄ O--) _w H, (--C ₃ H ₆ O--) _w H, (--C ₂ H ₄ O) _w --R ', (C ₃ H ₆ O) _w --R', R ', and w is an integer greater than 1 and less than 200.

This disclosure also provides a method of metalizing a polymer surface (eg, a surface of a non-conductive plastic). Within the scope of this method, according to an embodiment of the present disclosure, the plastic surface of one plastic product or the plastic surfaces of several plastic products is metallized.

Coating metal polymer surfaces (also known as polymer plating or polymer metallization) has become increasingly important. With polymer electroplating, laminates are produced that combine the advantages of polymers and metals. Compared to metal parts, the use of polymer parts can achieve significant weight savings. Electroplating of polymer moldings is usually performed for modification purposes, EMI masking, or surface property modification.

This section begins with a description of the most commonly used prior art processes used to produce metallized plastic products. It then focuses on issues related to this prior art process. This discussion then discusses the process and resulting product that overcomes all of these issues.

In prior art processes for metallized polymer parts, these parts were often fixed in a frame and contacted with a number of different processing fluids in a specific process sequence. As a first step, the plastic is typically pretreated to remove impurities, such as grease, from the surface. Subsequently, the surface is roughened using an etching process to ensure sufficient adhesion of the subsequent metal layer to the polymer surface. In etching operations, it is particularly important to form a uniform structure in the form of depressions (such as surface openings or micro holes) on the plastic surface. Subsequently, the roughened surface is treated with an activator to form a catalytic surface for subsequent chemical metallization or electroless plating. For this purpose, an ion-generating activator or colloidal system is used.

In prior art procedures, a plastic surface for activation with an ion generating system was first treated with tin (II) ions, after which a strongly adhered tin oxide hydrate gel was produced and rinsed with water. In a subsequent treatment with a palladium salt solution, a palladium core is formed on the surface by a redox reaction with a tin (II) species. These palladium nuclei have a catalytic effect on chemical metallization. For activation with a colloidal system, colloidal palladium solutions are usually used. These solutions are formed by reacting palladium chloride with tin (II) chloride in the presence of excess hydrochloric acid.

After activation, the plastic parts are typically chemically metallized first using a metastable solution of a metallization bath. These baths usually contain the metal to be deposited in the form of a salt in an aqueous solution and a reducing agent for the metal salt. When a chemical metallization bath is in contact with a metal core (such as a palladium seed) on a plastic surface, a metal is formed by reduction, and the metal is deposited on the surface as a strongly adherent layer. Chemical metallization steps are commonly used to deposit copper, nickel or nickel alloys with phosphorus and / or boron.

The chemically metallized polymer surface can then be further electrolytically deposited with a metal layer. Typically, the electrolytic deposition of a copper layer or another nickel layer is performed before electrochemically applying the required modified chromium layer.

There are several major issues associated with this prior art process for producing metallized polymer articles:

1) The process is tedious and involves many steps: pretreatment, chemical etching, activation, chemical metallization, and electrolytic deposition of multiple metal layers (hence multiple steps).

2) The most commonly used etchant is chromium-sulfuric acid or chromo-sulfuric acid (chromic trioxide in sulfuric acid), especially for ABS (acrylonitrile-butadiene-styrene copolymerization) Material) or polycarbonate. Chromium-sulfuric acid is very toxic and requires special precautions during the etching process, after treatment and disposal. Due to the chemical processes in the etching process, such as the reduction of the chromium compounds used, the chromium-sulfuric acid etchant is used up and is generally not reusable.

3) The key process step of plastic plating is to create micro holes so that the metal can adhere to the plastic surface. These microholes are used as a starting point for metal core growth in subsequent metallization steps. Generally, these microholes have a size of about 0.1 μm to 10 μm. In particular, these micro holes show a depth in the range of 0.1 μm to 10 μm (ie, the degree from the plastic surface toward the inside). Unfortunately, surface microholes can be stress concentration sites that weaken the strength of plastic parts.

4) After etching or roughening the plastic surface, first activate the surface with colloidal palladium or ion-forming palladium. In the case of a colloidal process, this activation is followed by removal of the protective tin colloid, or in the case of an ionic process, this activation is followed by reduction to the elemental palladium. Subsequently, copper or nickel is chemically deposited on the plastic surface as a conductive layer. After that, plating or metallization is performed. In practice, this direct metallization of plastic surfaces is only suitable for certain plastics. If it is impossible to sufficiently roughen the plastic or form suitable micro-holes by etching the surface of the plastic, the functionally strong adhesion of the metal layer to the surface of the plastic cannot be guaranteed. Therefore, in the prior art process, the amount of plastic that can be coated is greatly limited.

5) Precious metals such as palladium are very expensive.

This disclosure provides a graphene-mediated method for producing metallized polymer articles. The disclosed method overcomes all of these problems.

In some embodiments, the method includes: (a) treating the surface of the polymer part as needed to prepare a surface-treated polymer part (this procedure is optional, because the graphene dispersion itself is capable of pre-treating the polymer Surface); (b) provide a graphene dispersion (also referred to herein as a graphene / conductive filler mixture dispersion), the dispersion comprising a plurality of graphene flakes (functionalized or unfunctionalized) dispersed in a liquid medium And conductive fillers (in the form of nanofibers, nano particles, nanowires, etc.), bringing the surface-treated or untreated polymer part into contact with the graphene dispersion, and bringing the graphene sheets And the conductive filler is deposited on the surface of the surface-treated polymer part, wherein the graphene sheets and the conductive filler are bonded to the surface to form a bonded graphene sheet covering (partially or completely) the surface of the polymer part / Conductive filler layer; and (c) chemically, physically, electrochemically or electrolytically depositing a metal layer on the surface of the surface of the covered polymer part to form the surface metallization Polymeric article. Once again, step (a) is as needed in the disclosed method.

As an example, the polymer component may be selected from the group consisting of polyethylene, polypropylene, polybutene, polyvinyl chloride, polycarbonate, acrylonitrile-butadiene-styrene (ABS), polyester, polyvinyl alcohol, and polyvinylidene. Polyethylene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene ether (PPO), polymethyl methacrylate (PMMA), copolymers thereof, polymer blends thereof, or combinations thereof. The polymer may also be selected from the group consisting of phenolic resin, polyfurfuryl alcohol, polyacrylonitrile, polyimide, polyfluorene, polyoxadiazole, polybenzoxazole, polybenzodioxazole, polythiazole, and polybenzo. Thiazole, polybenzodithiazole, poly (p-phenylene vinylene), polybenzimidazole, polybenzodiimidazole, a copolymer thereof, a polymer blend thereof, or a combination thereof.

In some embodiments, step (a) is omitted from the process because the liquid medium in the graphene dispersion is generally capable of removing grease and other undesired species from the surface of the polymer part. Some liquid media in graphene dispersions can further provide an etching effect to produce small surface depressions (mild etching conditions) with a depth of <0.1 μm. In these cases, the entire process requires only three simple steps.

In certain embodiments, step (a) may include the step of subjecting the surface of the polymer component to abrasion treatment, etching treatment, or a combination thereof. In some embodiments, step (a) includes the step of subjecting the surface of the polymer component to an etching treatment using an etchant selected from an acid, an oxidant, a metal salt, or a combination thereof. Preferably, step (a) includes a step of subjecting the surface of the polymer member to an etching treatment without using chromic acid or chromic sulfuric acid. More preferably, step (a) includes the step of subjecting the surface of the polymer part to an etching treatment using an etchant selected from an acid, an oxidant, a metal salt, or a combination thereof under mild etching conditions, wherein the etching is performed at a sufficiently low level The temperature is performed for a short period of time so as not to generate micro holes having an average size greater than 0.1 μm.

The mild etching mentioned in this disclosure means that "etching" or treating a plastic surface with an etching solution occurs at low temperatures and / or within a short period of time at a low etching solution concentration. When one of the foregoing three conditions is satisfied, mild etching conditions can be achieved. The low temperature mentioned in this disclosure means that the maximum temperature is 40 ° C, preferably <30 ° C, and most preferably from 15 ° C to 25 ° C. At the above-mentioned low temperature, the pretreatment with the etching solution is performed in a period of 3 minutes to 15 minutes, preferably 5 minutes to 15 minutes, and even more preferably 5 minutes to 10 minutes. The higher the temperature, the shorter the processing time. However, if the selected processing time is appropriately short, mild etching conditions can be achieved even at temperatures exceeding 40 ° C. According to an embodiment of the present disclosure, the etching treatment is performed at a temperature of 40 ° C to 95 ° C, preferably 50 ° C to 70 ° C, for 15 seconds to 5 minutes, and preferably for 0.5 minutes to 3 minutes. Processing time. In practice, the process temperature and / or process time is selected according to the type of etching solution used.

Mild etching also means that, contrary to the above-mentioned prior art processes, no roughening of the polymer surface or generation of micro holes in the polymer surface is performed. Micro-holes created by etching according to prior art processes typically have a diameter or depth within a size range of 0.1 μm to 10 μm. In the present disclosure, the etching conditions are adjusted so that only small openings or holes are created in the polymer surface, these small openings or holes having a diameter of <0.1 μm, preferably <0.05 μm and especially depth. In this regard, depth means the degree of openings / channels from the surface of the polymer to the interior of the polymer. Therefore, the etching in the classical sense in the case of the prior art process is not performed here. In the process of this disclosure in which step (a) is eliminated, the liquid medium in the graphene dispersion can generally produce openings or holes having a size of <0.1 μm. Contrary to what was taught in the prior art, we unexpectedly observed that the disclosed graphene-mediated metallization method does not need to generate micro-holes larger than 0.1 μm in size. This method works even on highly smooth surfaces.

In step (a), the etching treatment may be performed with an etching solution and / or by plasma treatment or by plasma etching, ion bombardment, or the like.

Preferably, the etching solution used for etching contains at least one oxidizing agent. Mild etching within the scope of this disclosure also means that the oxidant is used at a low concentration. Permanganate and / or persulfate and / or periodate and / or peroxide can be used as oxidants. According to an embodiment of the present disclosure, the etching is performed by an acid etching solution, which includes at least one oxidizing agent. Instead of using a separate etching solution, an oxidant and / or an acid or alkaline solution (discussed below) can be added to the graphene dispersion, and as such, steps (a) and (b) are basically combined into a single step .

Preferably, an aqueous etching solution containing permanganate and phosphoric acid (H ₃ PO ₄ ) and / or sulfuric acid is used. Potassium permanganate can be used as a permanganate. It is very preferable to use an acid etching solution which contains only phosphoric acid or mainly contains phosphoric acid and only a small amount of sulfuric acid.

According to another embodiment of the present disclosure, the etching treatment is performed by using an alkaline aqueous solution containing a permanganate. Here again, it is preferred to use potassium permanganate. The alkaline aqueous solution may contain a lye. The type of etching solution used depends on the type of polymer to be treated. A preferred concentration of the oxidant in the etching solution is from 0.05 mol / l to 0.6 mol / l. Preferably, the etching solution contains permanganate or persulfate in the range of 0.05 mol / l to 0.6 mol / l. The etching solution may contain periodate or hydrogen peroxide from 0.1 mol / l to 0.5 mol / l. The preferred permanganate ratio is 1 g / l up to the solubility limit of permanganate, more preferably potassium permanganate. The permanganate solution preferably contains 2 g / l to 15 g / l of permanganate, and more preferably 2 g / l to 15 g / l of potassium permanganate. The permanganate solution may contain a wetting agent.

Mild etching can also be achieved by using a dilute persulfate or periodate solution or a dilute peroxide solution (either as a separate etching solution or as part of a graphene dispersion). It is preferable to perform a mild etching process using an etching solution while stirring the solution. After gentle etching, the plastic surface is rinsed in water, for example for 1 to 3 minutes. According to a preferred embodiment of the present disclosure, the treatment with the metal salt solution is performed at a temperature of <30 ° C, preferably between 15 ° C and 25 ° C (including room temperature). In practice, treatment with a metal salt solution is performed without stirring. The preferred processing time is 30 seconds to 15 minutes, and more preferably 3 minutes to 12 minutes. Preferably, a metal salt solution is used, the solution having a pH value between 7.5 and 12.5, preferably adjusted to between 8 and 12. Preferably, a metal salt solution containing ammonia and / or at least one amine is used. The above-mentioned pH adjustment can be achieved with the help of ammonia, and it is preferable to use an alkali metal salt solution. Metal salt solutions containing one or more amines can also be used. For example, the metal salt solution may contain monoethanolamine and / or triethanolamine. Treatment with a metal salt solution means that the surface of the polymer part is preferably immersed in the metal salt solution.

In certain embodiments, step (b) includes soaking or dipping a surface-treated or untreated polymer part in a graphene dispersion, and then removing the polymer part from the graphene dispersion to achieve A graphene sheet and a conductive filler are deposited on the surface of the surface-treated polymer part, wherein the graphene sheet and the conductive filler are bonded to the surface to form a layer of the combined graphene sheet / conductive filler. Alternatively, the graphene dispersion can be simply sprayed on the surface of the polymer part, allowing the liquid components to evaporate, and allowing the adhesive (if present) to cure or solidify.

If present, the adhesive resin layer may be formed of an adhesive resin composition containing the adhesive resin as a main component. The binder resin composition may include a curing agent and a coupling agent, and a binder resin. Examples of the binder resin may include ester resins, urethane resins, urethane resins, acrylic resins, and urethane acrylic resins, and specifically include neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid And terephthalic acid ester resin. The curing agent may be present in an amount of 1 to 30 parts by weight based on 100 parts by weight of the binder resin. The coupling agent may include an epoxy silane compound.

The curing of the adhesive layer can be performed via heat, UV or ionizing radiation. This may involve heating the layer coated with the heat-curable composition to a temperature of at least 70 ° C, preferably 90 ° C to 150 ° C, for at least 1 minute (typically up to 2 hours, and more typically from 2 minutes to 30 minutes) in order to form a hard coating.

You can use dipping, coating (for example, doctor blade coating, rod coating, slot die coating, comma coating, reverse roll coating, etc.), roll-to-roll process, inkjet printing, screen printing, Microcontact, gravure coating, spraying, ultrasonic spraying, electrostatic spraying, and flexographic printing expose the surface of polymer parts to graphene or CNT dispersions. The thickness of the hard coat layer or the adhesive layer is usually about 1 nm to 10 μm, and preferably 10 nm to 2 μm.

For the heat-curable resin, the polyfunctional epoxy monomer may be preferably selected from the group consisting of diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol Polyglycidyl ether (such as pentaerythritol tetraglycidyl ether), or a combination thereof. The bifunctional or trifunctional epoxy monomer can be selected from the group consisting of trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, Triphenylolmethane triglycidyl ether, triphenol triglycidyl ether, tetrahydroxyphenylethane triglycidyl ether, tetrahydroxyphenylethane tetraglycidyl ether, p-aminophenol triglycidyl ether 1,2,6-hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxy triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerol Alcohol triglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dipropylene glycol diglycidyl ether Ether, polypropylene glycol diglycidyl ether, dibromo neopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (3,4-epoxycyclohexane) methyl 3,4-epoxycyclohexyl Formates and mixtures.

In certain embodiments, the heat-curable composition of the present disclosure advantageously further contains at least one surface-active compound in a small amount, preferably from 0.05% to 0.20% by weight. Surfactants are important for good wetting of the substrate, resulting in a satisfactory final hard coating.

UV radiation-curable resins and lacquers useful in the adhesive layer used in this disclosure are photopolymerizable monomers and oligomers derived from polyfunctional compounds such as acrylate and methacrylate oligomers ( The term "(meth) acrylate" as used herein refers to those of acrylates and methacrylates)), such as polyols having (meth) acrylate functional groups and their derivatives, such as ethoxylated Trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tetra (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, or neopentyl glycol di (methyl) ) Acrylates and mixtures thereof, and derived from low molecular weight polyester resins, polyether resins, epoxy resins, polyurethane resins, alkyd resins, spiral resins, epoxy acrylates, polybutadiene resins, and polysulfides alcohol- Acrylate and methacrylate oligomers of polyolefin resins.

UV polymerizable monomers and oligomers are coated (eg, after exiting from the dip) and dried, and then exposed to UV radiation to form an optically transparent, cross-linked, wear-resistant layer. The preferred UV curing dose is between 50 mJ / cm ² and 1000 mJ / cm ² .

UV curable resins are also typically ionizing radiation curable. Ionizing radiation-curable resins may contain relatively large amounts of reactive diluents. Reactive diluents useful herein include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, vinyltoluene, and N-vinylpyrrolidone; and Multifunctional monomers such as trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, or neopentyl glycol di (meth) acrylate.

In the disclosed method, step (c) may include immersing the graphene-bonded polymer part in a metallization bath. The high conductivity of the deposited graphene sheet easily enables one or more metal layers to be plated on the surface of the graphene / conductive filler-coated polymer part.

Alternatively and advantageously, the final metallization step can be performed by an electroless plating method using no expensive precious metal solution. This step may include dipping (soaking) the graphene / conductive filler-coated polymer part in an electroless plating bath containing a metal salt (a salt of a metal such as Cu, Ni, or Co is expected) dissolved in a liquid medium ) (For example, CuSO ₄ soluble in water or NiNO ₃ soluble in water). This dipping procedure typically requires a contact time from 3 seconds to 30 minutes.

The copper metal plating bath (or nickel plating bath) may contain a copper salt (or Ni salt) and an additive depletion-inhibiting compound. Additive depletion inhibiting compounds may include methylmethylene, methylamidine, tetramethylenemethylene, thioglycolic acid, 2 (5H) thienone, 1,4-dithia, trans-1,2-dithia, tetra Hydrothiophene-3-one, 3-thiophenemethanol, 1,3,5-trithiane, 3-thiopheneacetic acid, thiotetraic acid, crown thioether, tetrapyrid, dipropyltrisulfide, Bis (3-triethoxysilylpropyltetrasulfide, dimethyltetrasulfide, methyl methanethiosulfate, (2-sulfoethyl) methane, p-tolyldisulfene, p-toluene Dioxin, bis (benzenesulfonyl) sulfide, 4- (chlorosulfonyl) benzoic acid, isopropylsulfonyl chloride, 1-propanesulfonyl chloride, lipoic acid, 4-hydroxybenzenesulfonic acid, benzene Vinyl fluorene, or a mixture thereof.

Alternatively, physical vapor deposition, sputtering, plasma deposition, etc. may be selected to complete the final metallization process.

The preparation of graphene sheets and graphene dispersions is described as follows: Carbon is known to have five unique crystal structures, including diamond, fullerene (0-D nano-graphite material), carbon nanotubes, or carbon nanofibers ( 1-D nano graphite material), graphene (2-D nano graphite material), and graphite (3-D graphite material). Carbon nanotube (CNT) refers to a tubular structure that grows in single or multiple walls. Carbon nanotubes (CNT) and carbon nanofibers (CNF) have a diameter of about several nanometers to several hundred nanometers. Its longitudinal, hollow structure gives the material unique mechanical, electrical, and chemical properties. CNT or CNF is one-dimensional nano-carbon or 1-D nano-graphite material.

As early as 2002, our research team pioneered the development of graphene materials and related production processes: (1) BZ Jang and WC Huang, "Nano-scaled Graphene Plates", US Patent No. 7,071,258 (07/04/2006), application submitted on October 21, 2002; (2) BZ Jang et al. "Process for Producing Nano-scaled Graphene Plates [Process for Producing Nano-scaled Graphene Plates]", US Patent Application No. 10 / 858,814 (06/03/2004) (US Patent Publication No. 2005/0271574); and (3) BZ Jang, A. Zhamu and J. Guo, "Process for Producing Nano-scaled Platelets and Nanocomposites [Process for producing nano-scale platelets and nano-composites] ", US Patent Application No. 11 / 509,424 (08/25/2006) (US Patent Publication No. 2008-0048152).

A single-layer graphene sheet is composed of carbon atoms occupying a two-dimensional hexagonal lattice. Multi-layer graphene is a platelet composed of more than one graphene plane. Individual single-layer graphene sheets and multilayer graphene platelets are collectively referred to herein as nanographene platelets (NGP) or graphene materials. NGP includes primary graphene (basically 99% carbon atoms), micro-graphene oxide (<5 wt% oxygen), graphene oxide (≥ 5 wt% oxygen), microfluorinated graphene (<5 wt% Fluorine), fluorinated graphene (≥ 5 wt% fluorine), other halogenated graphene, and chemically functionalized graphene.

NGP has been found to have a range of unusual physical, chemical and mechanical properties. For example, graphene was found to exhibit the highest inherent strength and highest thermal conductivity of all existing materials. Although it is not anticipated that actual electronic device applications of graphene (for example, replacing Si as a skeleton in transistors) will occur in the next 5-10 years, it is used as a nanofiller in composite materials and as an electrode material in energy storage devices. The application is coming soon. The availability of a large number of processable graphene sheets is critical to the successful development of graphene composites, energy and other applications.

Recently, we reviewed the processes for producing NGP and NGP nanocomposites [Bor Z. Jang and A Zhamu, "Processing of Nano Graphene Platelets (NGPs) and NGP Nanocomposites: A Review [Nano Graphene Platelet (NGP) and Processing of NGP Nanocomposites: A Review] ", J. Materials Sci. [Journal of Materials Science] 43 (2008) 5092-5101].

A very useful method (Figure 1) requires treating natural graphite powder with an intercalating agent and an oxidizing agent (for example, concentrated sulfuric acid and nitric acid, respectively) to obtain a graphite intercalation compound (GIC) or actually graphite oxide (GO). [William S. Hummers, Jr. et al., Preparation of Graphitic Oxide [Journal of the American Chemical Society], 1958, p. 1339. ] Prior to intercalation or oxidation, graphite has a graphene interplanar spacing of approximately 0.335 nm (L _d = ½ d ₀₀₂ = 0.335 nm). In the case of intercalation and oxidation treatment, the inter-graphene spacing increases to a value typically greater than 0.6 nm. This series of graphite materials undergoes the first expansion stage during this chemical route. The resulting GIC or GO is then subjected to further expansion (often referred to as expansion) using a thermal shock exposure method or a solution-based ultrasound treatment assisted graphene layer expansion method.

In the thermal shock exposure method, GIC or GO is exposed to high temperatures (typically 800 ° C-1,050 ° C) for a short period of time (typically 15 to 60 seconds) to expand or swell the GIC or GO to form an expanded or Further expanded graphite, which is typically in the form of a "graphite worm" composed of graphite flakes still interconnected with each other. This thermal shock procedure can produce some discrete graphite flakes or graphene sheets, but usually most of the graphite flakes remain interconnected. Typically, the expanded graphite or graphite worms are then subjected to a flake separation treatment using air milling, mechanical shearing, or ultrasonic treatment in water. Therefore, method 1 basically requires three different procedures: first expansion (oxidation or intercalation), further expansion (or "expansion"), and separation.

In a solution-based separation method, a swollen or puffed GO powder is dispersed in water or an aqueous alcohol solution and subjected to ultrasonic treatment. It is important to note that in these processes, after the intercalation and oxidation of graphite (ie, after the first expansion) and typically after the thermal shock of the resulting GIC or GO is exposed (after the second expansion) Sonic processing. Alternatively, the GO powder dispersed in water is subjected to ion exchange or lengthy purification procedures in such a way that the repulsive force between the ions existing in the space between the planes exceeds the van der Waals force between graphenes, resulting in The ene layer was separated.

In the above examples, the starting material used to prepare the graphene sheet or NGP is a graphite material, which may be selected from the group consisting of natural graphite, artificial graphite, graphite oxide, fluorinated graphite, graphite fiber, and carbon fiber , Carbon nanofibers, carbon nanotubes, mesocarbon microbeads (MCMB) or carbon microspheres (CMS), soft carbon, hard carbon, and combinations thereof.

Graphite oxide can be kept long enough by dispersing or immersing a layered graphite material (eg, natural flake graphite or a powder of synthetic graphite) in an oxidant at a desired temperature (typically 0 ° C to 70 ° C). The oxidant is typically a mixture of an intercalator (such as concentrated sulfuric acid) and an oxidant (such as nitric acid, hydrogen peroxide, sodium perchlorate, potassium permanganate) for a period of time (typically 4 hours to 5 days). . The resulting graphite oxide particles are then washed several times with water to typically adjust the pH to 2-5. The resulting suspension of graphite oxide particles dispersed in water is then subjected to ultrasonic treatment to produce a dispersion of separated graphene oxide sheets dispersed in water. A small amount of reducing agent (such as Na ₄ B) can be added to obtain a reduced graphene oxide (RDO) sheet.

In order to reduce the time required to generate the precursor solution or suspension, the graphite can be oxidized to a certain degree for a short period of time (for example, 30 minutes to 4 hours) to obtain a graphite intercalation compound (GIC). The GIC particles are then exposed to thermal shock, preferably in a temperature range of 600 ° C to 1,100 ° C, typically for 15 seconds to 60 seconds, to obtain expanded graphite or graphite worms, making them as needed (but Preferably, it is subjected to mechanical shearing (for example, using a mechanical shearing machine or an ultrasonic wave generator) to break up the graphite flakes constituting the graphite worm. The separated graphene sheets (after mechanical shearing) or unbroken graphite worms or individual graphite flakes are then redispersed in water, acid, or organic solvents and ultrasonically treated to obtain a graphene dispersion.

The primary graphene material is preferably produced by one of the following three processes: (A) intercalating the graphite material with a non-oxidizing agent, and then performing thermal or chemical expansion treatment in a non-oxidizing environment; (B) subjecting the graphite material to ultra-thin Critical fluid environment for penetration and expansion between graphene layers; or (C) dispersing graphite material in powder form into an aqueous solution containing a surfactant or dispersant to obtain a suspension and subjecting the suspension to direct ultrasonic treatment to A graphene dispersion was obtained.

In the procedure (A), particularly preferred steps include (i) using a graphite material selected from an alkali metal (such as potassium, sodium, lithium, or cesium), an alkaline earth metal, or an alloy or mixture of an alkali metal or an alkaline earth metal, or Eutectic non-oxidant intercalation; and (ii) chemical expansion (for example, by soaking potassium intercalated graphite in an ethanol solution).

In procedure (B), the preferred steps include immersing the graphite material in a supercritical fluid such as carbon dioxide (for example, at a temperature T> 31 ° C and a pressure P> 7.4 MPa) and water (for example, at T> 374 ° C and P> 22.1 MPa) for a period of time sufficient to allow permeation (temporary intercalation) of graphene layers. A sudden decompression is then performed after this step to puff the individual graphene layers. Other suitable supercritical fluids include methane, ethane, ethylene, hydrogen peroxide, ozone, water oxides (water containing high concentrations of dissolved oxygen), or mixtures thereof.

In the procedure (C), the preferred steps include (a) dispersing particles of the graphite material in a liquid medium containing a surfactant or dispersant therein to obtain a suspension or slurry; and (b) dispersing the suspension Or the slurry is exposed to a certain level of ultrasound (commonly referred to as a process of ultrasound treatment) for a period of time long enough to produce a separate graphene sheet dispersed in a liquid medium such as water, alcohol, or an organic solvent ( Graphene dispersion of non-oxidized NGP).

An NGP with an oxygen content of not more than 25% by weight, preferably less than 20% by weight, and even more preferably less than 5% can be produced. Typically, the oxygen content is between 5 and 20% by weight. The oxygen content can be determined using chemical element analysis and / or X-ray photoelectron spectroscopy (XPS).

The layered graphite material used in the prior art process for the production of GIC, graphite oxide, and subsequently extruded graphite, flexible graphite flakes, and graphene flakes is natural graphite in most cases. However, this disclosure is not limited to natural graphite. The starting material can be selected from the group consisting of natural graphite, artificial graphite (for example, highly oriented pyrolytic graphite, HOPG), graphite oxide, fluorinated graphite, graphite fiber, carbon fiber, carbon nanofiber, and carbon nano. Tubes, mesocarbon microbeads (MCMB) or carbon microspheres (CMS), soft carbon, hard carbon, and combinations thereof. All of these materials contain graphite crystallites, which are composed of graphene planar layers stacked or bonded together via van der Waals forces. In natural graphite, multiple graphene planar stacks (where the planar orientation of graphene varies with the stack) are gathered together. In carbon fibers, the graphene plane is generally oriented in a preferred direction. Generally speaking, soft carbon is a carbonaceous material obtained by carbonization of liquid aromatic molecules. Their aromatic rings or graphene structures are substantially parallel to each other, enabling further graphitization. Hard carbon is a carbonaceous material obtained from aromatic solid materials such as polymers, such as phenolic resins and polyfurfuryl alcohol. Their graphene structure is relatively randomly oriented, and therefore it is difficult to achieve further graphitization even at temperatures above 2,500 ° C. However, graphene sheets do exist in these carbons.

Fluorinated graphene or graphene fluoride is used herein as an example of a group of halogenated graphene materials. There are two different methods that have been followed to produce fluorinated graphene: (1) fluorination of pre-synthesized graphene: this method requires treatment with a fluorinating agent such as XeF ₂ or F-based plasma by mechanical Puffing or graphene prepared by CVD growth; (2) Puffing of multilayer fluorinated graphite: both mechanical puffing and liquid-phase puffing of fluorinated graphite can be easily achieved [F. Karlicky et al. Family of Graphene Derivatives "[Halogenized graphene: a fast-growing family of graphene derivatives] ACS Nano [ACS Nano], 2013, 7 (8), pages 6434-6464].

The interaction of F ₂ and graphite at high temperature results in covalent fluorinated graphite (CF) _n or (C ₂ F) _n , while the graphite intercalation compound (GIC) is formed at low temperature C _x F (2 ≤ x ≤ 24) . In (CF) _n , the carbon atom system sp3 is hybridized and thus the fluorocarbon layer system is corrugated and consists of a trans-linked cyclohexane chair. In (C ₂ F) _n , only half of the C atoms are fluorinated, and each pair of adjacent carbon flakes are linked together by a covalent CC bond. A systematic study of the fluorination reaction shows that the obtained F / C ratio depends greatly on the fluorination temperature, the partial pressure of fluorine in the fluorinated gas, and the physical properties of the graphite precursor, including the degree of graphitization, particle size, and Specific surface area. In addition to fluorine (F ₂ ), other fluorinating agents can be used, although most existing literature relates to fluorination with F ₂ gas (sometimes in the presence of fluoride).

In order to expand the layered precursor material into a state of a single single graphene layer or few layers, it is necessary to overcome the attractive force between adjacent layers and further stabilize these layers. This can be achieved by covalently modifying the graphene surface with functional groups or by non-covalent modification using specific solvents, surfactants, polymers or donor-acceptor aromatic molecules. The liquid-phase expansion process includes ultrasonically treating fluorinated graphite in a liquid medium to produce fluorinated graphene sheets dispersed in the liquid medium. The resulting dispersion can be used directly for graphene deposition on the surface of polymer parts.

Nitriding of graphene can be performed by exposing a graphene material (such as graphene oxide) to ammonia at a high temperature (200 ° C-400 ° C). Graphene nitride can also be formed at lower temperatures by hydrothermal methods; for example, by sealing GO and ammonia in an autoclave and then raising the temperature to 150 ° C -250 ° C. Other methods of synthesizing nitrogen-doped graphene include nitrogen plasma treatment on graphene, arc discharge between graphite electrodes in the presence of ammonia, ammonolysis of graphene oxide under CVD conditions, and graphite oxidation at different temperatures Hydrolysis of olefins and urea.

For the purpose of limiting the scope of patent application for this application, NGP or graphene materials include single and multiple layers (typically less than 10 layers, few layers of graphene), primary graphene, graphene oxide, reduced graphene oxide (RGO), Discretization of fluorinated graphene, chlorinated graphene, brominated graphene, graphene iodide, hydrogenated graphene, nitrided graphene, chemically functionalized graphene, doped graphene (eg, doped with B or N)的 片 / 片 晶。 The sheet / sheet crystal. Primary graphene has substantially 0% oxygen. RGO typically has an oxygen content of 0.001% to 5% by weight. Graphene oxide (including RGO) may have 0.001 to 50% by weight of oxygen. With the exception of virgin graphene, all graphene materials have non-carbon elements (eg, O, H, N, B, F, Cl, Br, I, etc.) from 0.001% to 50% by weight. These materials are referred to herein as non-native graphene materials. The graphenes disclosed herein may contain native or non-native graphene, and the methods disclosed allow this flexibility. These graphene sheets can all be chemically functionalized.

Graphene sheets have a considerable proportion of edges corresponding to the edge planes of graphite crystals. The carbon atoms in the edge plane are reactive and must contain some heteroatom or group to satisfy the carbon valence. In addition, there are many types of functional groups (such as hydroxyl and carboxyl groups) that naturally occur on the edges or surfaces of graphene sheets produced by chemical or electrochemical methods. Using methods known in the art, can be easily many functional chemical group (e.g., -NH _2, etc.) gives the graphene edges and / or surfaces.

In a preferred embodiment, the resulting functionalized graphene sheet (NGP) may have the following formula (e) in a broad sense: [NGP]-R _m , where m is the number of different functional group types (typically at Between 1 and 5), R is selected from SO ₃ H, COOH, NH ₂ , OH, R'CHOH, CHO, CN, COCl, halide, COSH, SH, COOR ', SR', SiR ' ₃ , Si ( --OR '-) _y R' _3-y , Si (-O--SiR ' _2- ) OR', R ", Li, AlR ' ₂ , Hg--X, TlZ ₂ and Mg-- X; where y is an integer equal to or less than 3, R 'is hydrogen, alkyl, aryl, cycloalkyl or aralkyl, cycloaryl or poly (alkyl ether), R "is fluoroalkyl, Fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate.

In order to make NGP an effective reinforcing filler in epoxy resins, the functional group -NH ₂ is of particular interest. For example, for a curing agent commonly used in epoxy resins, diethylene triamine (DETA), it has three -NH ₂ groups. If DETA is contained in the impact chamber, one of the three -NH ₂ groups can be bonded to the edge or surface of the graphene sheet, and the remaining two unreacted -NH ₂ groups will be available for subsequent contact with Epoxy reaction. This arrangement provides good interface bonding between the NGP (graphene sheet) of the composite material and the matrix resin.

Other useful chemical functional groups or reactive molecules may be selected from the group consisting of amidoamine, polyamidoamine, aliphatic amine, modified aliphatic amine, alicyclic amine, aromatic amine , Anhydride, ketimine, diethylene triamine (DETA), triethylene tetramine (TETA), tetra ethylene pentamine (TEPA), hexamethylene tetramine, polyethylen , Polyamine epoxy adducts, phenol hardeners, non-brominated curing agents, non-amine curing agents, and combinations thereof. These functional groups are polyfunctional and have the ability to react with at least two chemical species from at least two ends. Most importantly, they are able to bond to the edge or surface of graphene using one of their ends, and they can react with epoxide or epoxy at one or two other ends during the subsequent epoxy curing phase .

[NGP]-R _m described above can be further functionalized. The resulting graphene sheet includes a composition having the following formula: [NGP]-A _m , where A is selected from OY, NHY, O = C--OY, P = C--NR'Y, O = C--SY , O = C--Y, --CR'1--OY, N'Y or C'Y, and Y is a protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen , suitable functional groups, or an enzyme substrate, enzyme inhibitor or the transition state analog of an enzyme substrate or is selected from R '- OH, R' - NR '2, R'SH, R'CHO, R'CN ^{, R'X, R'N + (R '} ) 3 X -, R'SiR' 3, R'Si (- OR '-) y R' 3-y, R'Si (- O-- SiR ' _2- ) OR', R '-R ”, R'-N--CO, (C ₂ H ₄ O--) _w H, (--C ₃ H ₆ O--) _w H , (--C ₂ H ₄ O) _w --R ′, (C ₃ H ₆ O) _w --R ′, R ′, and w is an integer greater than 1 and less than 200. CNTs can be similarly functionalized.

NGP and conductive additives (such as carbon nanofibers) can also be functionalized to produce a composition having the formula: [NGP]-[R '-A] _m , where m, R', and A are as defined above. The composition of the present disclosure also includes NGP on which certain cyclic compounds are adsorbed. These include compositions of matter having the following formula: [NGP]-[X--R _a ] _m , where a is a number of zero or less, X is a polynuclear aromatic moiety, a polyheteronuclear aromatic moiety, or a metal A heteronuclear aromatic moiety, and R is as defined above. Preferred cyclic compounds are planar. More preferred cyclic compounds for adsorption are porphyrins and phthalocyanines. The adsorbed cyclic compound may be functionalized. Such compositions include compounds having the formula [NGP]-[X--A _a ] _m , where m, a, X and A are as defined above.

The functionalized NGP disclosed herein can be directly prepared by sulfonation, electrophilic addition to the surface of deoxygraphene platelets, or metallization. Graphene platelets can be processed before being contacted with a functionalizing agent. Such processing may include dispersing graphene platelets in a solvent. In some examples, the platelets can then be filtered and dried before contacting. A particularly useful type of functional group is the carboxylic acid moiety. If NGP is prepared from the acid intercalation route discussed previously, these carboxylic acid moieties naturally exist on the surface of the NGP. If carboxylic acid functionalization is required, NGP can be subjected to chlorate, nitric acid, or ammonium persulfate oxidation.

Carboxylic acid-functionalized graphene sheets or platelets are particularly useful because they can serve as a starting point for preparing other types of functionalized NGP. For example, an alcohol or amidine can be easily attached to the acid to obtain a stable ester or amidine. If the alcohol or amine is part of a di- or poly-functional molecule, other functional groups are left as pendant groups through O- or NH- linkages. These reactions can be carried out using any method developed as known in the art for esterification with alcohols or amines with amines. Examples of these methods can be found in G. W. Anderson et al., J. Amer. Chem. Soc. [American Chemical Society] 86, 1839 (1964), which is incorporated herein by reference in its entirety. Amine groups can be introduced directly onto graphite platelets by treating the platelets with nitric acid and sulfuric acid to obtain nitrated platelets, and then chemically reducing the nitrated form with a reducing agent such as sodium dithionite to obtain amine functionalization. Sheet of crystals.

The resulting graphene dispersion may be further added with an acid, a metal salt, an oxidizing agent, or a combination thereof to prepare a graphene-coated more reactive dispersion for a polymer part. Optionally, a binder resin may be added. In these cases, surface cleaning, etching and graphene coating can be done in one step. The polymer part can be simply dipped into the graphene solution for a few seconds to several minutes (preferably 5 seconds to 15 minutes), and then the polymer part is ejected from the graphene-liquid dispersion. After the liquid is removed (eg, via natural or forced evaporation), the graphene sheet is naturally coated and bonded to the surface of the polymer part.

In certain embodiments, the functionalized graphene sheets and / or conductive fillers can be pre-coated or modified with nanoscale particles of a catalytic metal that can catalyze a subsequent chemical metallization process. The catalytic metal is preferably in the form of discrete nanoscale particles or coatings having a diameter or thickness from 0.5 nm to 100 nm, and is preferably selected from the group consisting of cobalt, nickel, copper, iron, manganese, tin, Zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof. Alternatively, the catalytic metal may initially be in the form of a precursor (eg, as a metal salt), which is then converted into a nano-scale metal deposited on the surface of graphene.

Accordingly, the present disclosure also provides metallized graphene dispersions (or graphene / conductive filler dispersions) for polymer surfaces. The graphene dispersion includes a plurality of graphene flakes and a conductive filler dispersed in a liquid medium, wherein the plurality of graphene flakes are selected from a primary graphene material having substantially 0% non-carbon elements or having To 25% by weight of a non-carbon element non-native graphene material of a single or few layers of graphene sheet, wherein the non-native graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated Graphene, graphene bromide, graphene iodide, graphene hydride, graphene nitride, doped graphene, chemically functionalized graphene, or a combination thereof, and wherein the dispersion further comprises one selected from the group consisting of One or more species: (i) a binder resin dissolved or dispersed in the liquid medium, wherein the weight ratio of the binder to graphene is from 1/5000 to 1/10; (ii) selected from acids, oxidants, metal salts Etchant, or a combination thereof; (iii) nanoscale particles or coatings of a catalytic metal having a diameter or thickness from 0.5 nm to 100 nm, the catalytic metal being selected from the group consisting of cobalt, nickel, copper, iron, manganese, tin , Zinc, lead, bismuth, silver, gold, palladium Platinum, alloys, or combinations thereof; or (iv) combinations thereof.

Once the graphene sheet is bonded to the surface of the polymer part, step (c) in the disclosed method may include immersing the graphene / conductive filler-bound polymer part in a metallizing bath for electroless plating of the metal ( Chemical metallization). It is very unexpected that the graphene surface itself (even without transition metals or noble metals) can promote the conversion of some metal salts into metals deposited on the graphene surface. This will eliminate the need for expensive noble metals (such as palladium or platinum) as cores for subsequent chemical growth of metal crystals, as required by prior art processes.

The high conductivity and high specific surface area of the deposited graphene sheet (which can cover the wide surface area of the polymer part) enables one or more metal layers to be plated on the surface of the graphene-coated polymer part. It has also been found that graphene sheets deposited on the surface of polymer components significantly enhance the strength, hardness, durability, and scratch resistance of the deposited metal layer.

Alternatively, physical vapor deposition, sputtering, plasma deposition, etc. may be selected to complete the final metallization process.

Accordingly, the disclosed method produces a surface metallized polymer article including a polymer part having a surface, a plurality of graphene sheets coated on the surface of the polymer part, and a first layer of conductive filler. , And a second metallized layer deposited on the first layer, wherein the plurality of graphene sheets (functionalized or non-functionalized) include single-layer graphene sheets or few layers of graphene sheets (2-10 Graphene planes), wherein the plurality of graphene sheets are bonded to the surface of the polymer component with or without an adhesive resin.

This first layer typically has a thickness from 0.34 nm to 30 μm (preferably from 1 nm to 1 μm, and further preferably from 1 nm to 100 nm). The second layer preferably has a thickness from 0.5 nm to 1.0 mm, and more preferably from 1 nm to 10 μm. The doped graphene preferably comprises N-doped, boron-doped, phosphorus-doped graphene, or a combination thereof. The graphene sheet contains native graphene, and the first layer contains a binder resin that chemically bonds the graphene sheet to the surface of the polymer part. In certain alternative embodiments, the graphene sheet comprises a non-native graphene material having a non-carbon element content from 0.01% to 20% by weight, and these non-carbon elements include a member selected from the group consisting of oxygen, fluorine, chlorine, bromine, An element of iodine, nitrogen, hydrogen, or boron.

As some examples, the surface metallized polymer article may be selected from a faucet, a shower head, a pipe, a pipe, a connector, an adapter, a sink (such as a kitchen or bathroom sink), a bathtub cover, a spout, a sink cover, a bathroom accessory, or Kitchen accessories.

The polymer component may include plastic, rubber, thermoplastic elastomer, polymer matrix composite, rubber matrix composite, or a combination thereof. In certain embodiments, the polymer component comprises a thermoplastic, a thermosetting resin, an interpenetrating network, a rubber, a thermoplastic elastomer, a natural polymer, or a combination thereof. In certain preferred embodiments, the polymer component comprises a plastic selected from the group consisting of acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polycarbonate Esters, polyamides or nylons, polystyrene, polyacrylates, polyethylene, polypropylene, polyacetals, polyesters, polyethers, polyethers, polyetheretherketones (PEEK), polyfluorenes, polyphenylene ethers (PPO), polyvinyl chloride (PVC), polyimide, polyimide, polyurethane, polyurea, or a combination thereof.

In the surface metallized polymer article, the metal to be plated is preferably selected from the group consisting of copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, alloys thereof, or combinations thereof.

The graphene sheet can be further modified with nano-sized particles or coatings (having a diameter or thickness from 0.5 nm to 100 nm) of a catalytic metal selected from cobalt, nickel, copper, iron, manganese, tin, zinc , Lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof, and wherein the catalytic metal is different in chemical composition from the metal to be plated. The catalytic metal particles or coatings are covered by at least one layer of metal plating.

In some embodiments, the surface of the polymer component contains only small openings or holes having a diameter or depth of <0.1 μm before the first layer of graphene sheets are deposited.

In some embodiments, a plurality of graphene sheets are bonded to the surface of the polymer component with an adhesive resin, and the adhesive has a pressure ratio of 1/5000 to 1/10, preferably 1/1000 to 1/100. Graphene weight ratio.

The following examples are provided to illustrate some specific details regarding the best mode of practicing the present disclosure and should not be construed as limiting the scope of the invention.

Example 1 : Sulfuric acid intercalation and expanded graphene oxide from MCMB

MCMB (Mesophase Carbon Microbeads) is supplied by China Steel Chemical Co., Ltd. This material has a density of about 2.24 g / cm ³ and a median particle size of about 16 μm. MCMB (10 g) was intercalated with an acid solution (4: 1: 0.05 ratio of sulfuric acid, nitric acid, and potassium permanganate) for 48 hours. After the reaction was completed, the mixture was poured into deionized water and filtered. The intercalated MCMB was washed repeatedly in a 5% solution of HCl to remove most of the sulfate ions. The sample was then repeatedly washed with deionized water until the pH of the filtrate was neutral. The slurry was dried and stored in a vacuum oven at 60 ° C for 24 hours. The dried powder sample is placed in a quartz tube and inserted into a horizontal tube furnace preset at a required temperature of 800 ° C to 1,100 ° C for 30 to 90 seconds to obtain a graphene sheet. A certain amount of graphene sheet was mixed with water and treated with 60 W ultrasonic for 10 minutes to obtain a graphene dispersion.

A small amount was sampled, dried and studied by TEM, showing that most of the NGP was between 1 and 10 layers. The oxygen content of the resulting graphene powder (GO or RGO) is from 0.1% to about 25%, depending on the puffing temperature and time.

Several graphene dispersions are added with various acids, metal salts and oxidant species for metallization of polymers.

Example 2 : Oxidation and Puffing of Natural Graphite

According to Hummers' method [US Patent No. 2,798,878, July 9, 1957], by oxidizing graphite flakes at 30 ° C for 48 hours with sulfuric acid, sodium nitrate, and potassium permanganate at a ratio of 4: 1: 0.05. Preparation of graphite oxide. After the reaction was completed, the mixture was poured into deionized water and filtered. The sample was then washed with a 5% HCl solution to remove most of the sulfate ions and residual salts, and then repeatedly washed with deionized water until the pH of the filtrate was about 4. The intention is to remove all sulfuric acid and nitric acid residues from the graphite interstices. The slurry was dried and stored in a vacuum oven at 60 ° C for 24 hours.

The dried, intercalated (oxidized) compound was expanded by placing the sample in a quartz tube inserted in a horizontal tube furnace preset at 1,050 ° C to obtain highly expanded graphite. The extruded graphite was dispersed together with 1% surfactant in water in a flat-bottomed flask at 45 ° C, and the resulting suspension was subjected to ultrasonic treatment for a period of 15 minutes to obtain graphene oxide (GO) tablets. Dispersions.

Example 3 : Preparation of primary graphene

Primary graphene sheets are produced by using a direct ultrasonic process or a liquid phase expansion process. In a typical procedure, 5 g of graphite flakes ground to a size of about 20 μm are dispersed in 1,000 mL of deionized water (containing 0.1% by weight of a dispersant, Zonyl® FSO from DuPont) to obtain a suspension liquid. An 85 W ultrasonic energy level (Branson S450 ultrasonic generator) was used for the expansion, separation and size reduction of graphene sheets for a period of 15 minutes to 2 hours. The resulting graphene sheet is a native graphene that has never been oxidized and is oxygen-free and relatively free of defects.

Example 4 : Preparation of fluorinated graphene

We have used several processes to produce GF, but this article describes only one process as an example. In a typical procedure, highly expanded graphite (the HEG) was prepared by the intercalation compound С2F · x ClF _3. HEG is further fluorinated with chlorine trifluoride vapor to produce fluorinated highly expanded graphite (FHEG). The pre-cooled Teflon reactor was filled with 20 mL-30 mL of pre-cooled liquid ClF ₃ , and then the reactor was closed and cooled to liquid nitrogen temperature. Subsequently, no more than 1 g of HEG was placed in a container having holes for ClF ₃ gas to enter the reactor. After 7-10 days, a gray beige product with approximate formula C ₂ F was formed. The GF tablets were then dispersed in a halogenated solvent to form a suspension.

Example 5 : Preparation of graphitic nitride

The graphene oxide (GO) synthesized in Example 2 was finely ground with different proportions of urea, and the granulated mixture was heated (900 W) in a microwave reactor for 30 s. The product was washed several times with deionized water and dried under vacuum. In this method, graphene oxide is simultaneously reduced and doped with nitrogen. The products obtained with graphene / urea mass ratios of 1 / 0.5, 1/1, and 1/2 were named N-1, N-2, and N-3, respectively, and the nitrogen of these samples was determined by elemental analysis. The contents were 14.7 wt.%, 18.2 wt.%, And 17.5 wt.%, Respectively. These graphene nitride sheets remain dispersible in water.

Example 6 : Graphene-bound / activated ABS

The first set of several ABS plastic rectangular strips each having a surface of 50 cm ² was immersed in an etching solution consisting of 4 MH ₂ SO ₄ and 3.5 M CrO ₃ at 70 ° C. for 3 minutes. Rinse the bars with water. On a separate basis, a second set of several strips of the same size was used, but not etched.

Two sets of samples were immersed in the RGO-water solution prepared in Example 1 for a period of 30 seconds at 40 ° C, and then removed from the solution and dried in air. Subsequently, the RGO-bound ABS strip was copper-plated in a copper electrolyte containing sulfuric acid. We have unexpectedly observed that the method of the present disclosure can successfully metallize ABS and various plastics without etching. The bonded metal layer mediated by graphene sheets performed equally well in terms of surface hardness, scratch resistance, and durability to heating / cooling cycles.

Comparative Example 6a : Pd / Sn activated ABS

The first set of several ABS plastic rectangular strips each having a surface of 50 cm ² was immersed in an etching solution consisting of 4 MH ₂ SO ₄ and 3.5 M CrO ₃ at 70 ° C. for 3 minutes. Rinse the bars with water. On a separate basis, a second set of several strips of the same size was used, but not etched.

Two groups of samples were immersed in a solution containing Pd / Sn colloid at 40 ° C for a period of 5 minutes, which contained 250 mg / L of palladium, 10 g / L of tin (II), and 110 g / L of HCl. These samples were then rinsed in water and plated with copper in a copper electrolyte containing sulfuric acid. We have observed that the ABS plastic surface cannot be properly (uniformly) metalized without heavy etching, even when some large amounts of expensive rare metals (such as Pd) are implemented on the etched surface.

Example 7 : Graphene bound / activated high impact polystyrene (HIPS)

The first set of several HIPS plastic rectangular strips each having a surface of 50 cm ² was immersed in an etching solution consisting of 4 MH ₂ SO ₄ and 3.5 M CrO ₃ at 70 ° C. for 3 minutes. Rinse the bars with water. On a separate basis, a second set of several strips of the same size was used, but not etched.

Thereafter, the plastic product was spray-coated with a native graphene-adhesive solution containing 5 wt% of a graphene sheet and 0.01 wt% of an epoxy resin. After removing the liquid medium (acetone) and curing at 150 ° C for 15 minutes, the graphene sheet bonded well to the plastic surface.

After this treatment, the graphene-bound plastic article is subjected to electrochemical nickel plating. To this end, the article was treated for 15 minutes in Watts electrolyte, which contains 1.2 M NiSO ₄ .7H ₂ O, 0.2 M NiCl ₂ .6H ₂ O, and 0.5 MH ₃ BO ₃ . The initial current was 0.3 A / dm ² , and nickel plating was performed at 40 ° C.

Comparative Example 7a : Sulfide Activated High Impact Polystyrene (HIPS)

The first set of several HIPS plastic rectangular strips each having a surface of 50 cm ² was immersed in an etching solution consisting of 4 MH ₂ SO ₄ and 3.5 M CrO ₃ at 70 ° C. for 3 minutes. Rinse the bars with water. On a separate basis, a second set of several strips of the same size was used, but not etched.

Thereafter, the plastic product was treated in an ammonia solution containing 0.5 M CuSO ₄ .5H ₂ O for 30 seconds, the solution having a pH value of 9.5 and a temperature of 20 ° C. The plastic article was then immersed in distilled water for 20 seconds, and then treated with a sulfide solution containing 0.1 M Na ₂ S ₂ for 30 seconds at 20 ° C. After this treatment, the plastic product was washed again in cold water. This was followed by electrochemical nickel plating. To this end, the article was treated for 15 minutes in Watts electrolyte, which contains 1.2 M NiSO ₄ .7H ₂ O, 0.2 M NiCl ₂ .6H ₂ O, and 0.5 MH ₃ BO ₃ . The initial current was 0.3 A / dm ² , and nickel plating was performed at 40 ° C. We have observed that without heavy etching, the surface of HIPS plastics cannot be metallized uniformly using sulfide seeding methods. In contrast, the graphene-mediated method of the present invention enables almost all kinds of metals to be successfully plated on not only HIPS surfaces but also any other type of polymer surface.

Example 8 : Graphene-based polyurethane-based thermoplastic elastomer (TPE)

The TPE strip was immersed in an alkaline aqueous solution containing 5 g / L sodium hydroxide and 0.5 g / L GO for 15 minutes. The strips were then removed from the solution (actually a graphene dispersion), allowing the graphene oxide sheet to be applied to the TPE surface while removing water. Rinse off the remaining NaOH with water.

The GO-coated bars were subjected to electroless nickel plating at 30 ° C for 10 minutes in a nickel-containing electrolyte. On a separate basis, a Ni layer was electrochemically deposited directly onto the GO-coated TPE surface. Both methods were found to provide Ni layers with high hardness, scratch resistance and gloss. This simple, two-step process is surprisingly effective in providing a wide variety of metallized polymer articles.

In contrast, if strong chromic sulfuric acid is not used as an etchant to generate large-sized micro-holes (surface voids) with a depth greater than 0.3 μm, it is not possible to uniformly metalize TPE parts under the instructions of Pd / Sn catalyst seeds. This etched TPE sample was immersed in a Pd / Sn colloid-containing solution containing 80 mg / L palladium, 10 g / L tin (II), and 110 g / L HCl for 10 minutes at 30ºC. This Pd / Sn The catalyst is deposited on the large surface voids of the TPE.

Example 9 : Graphene-bonded glass fiber reinforced polyester composite

Catalytic metals can be deposited on the surface of graphene using a variety of processes: physical vapor deposition, sputtering, chemical vapor deposition, chemical reduction / oxidation, electrochemical reduction / oxidation, and the like. In this example, Co was used as a representative catalytic metal, and chemical oxidation / reduction from the solution was used to deposit nano particles on the graphene surface.

As the metal salt solution, a cobalt salt solution was used. The cobalt (II) salt solution contains 1 g / L to 10 g / L of CoSO ₄ .7H ₂ O and an oxidant, namely hydrogen peroxide. Graphene oxide flakes were dispersed in a solution to form a dispersion. Heating this dispersion causes at least a portion of the cobalt (II) to be oxidized to cobalt (III) by H ₂ O ₂ , and the cobalt (III) is deposited on the graphene surface upon further heating. Electrolytic direct metallization of the composite surface is then allowed. This composite surface was electroplated in a nickel bath in which an initial current density of 0.3 A / dm ² was used for electrochemical nickel plating, which was later increased to 3 A / dm ² . Electrochemical nickel plating is performed in Watts electrolyte at a processing time of 10 to 15 minutes at 30 ° C to 40 ° C. Watts electrolyte contains 1.2 M NiSO ₄ .7H ₂ O, 0.2 M NiCl ₂ .6H ₂ O, and 0.5 MH ₃ BO ₃ .

Example 10 : Functionalized graphene- and CNT-bonded polyetheretherketone (PEEK) and other polymer parts

The first set of several PEEK plastic rectangular strips each having a surface of 50 cm ² was immersed in an etching solution consisting of 4 MH ₂ SO ₄ and 3.5 M CrO ₃ at 70 ° C. for 3 minutes. Rinse the bars with water. Separately, a second set of several strips of the same size was used but not etched.

Subsequently, the plastic product is dipped into a functionalized graphene / CNT-binder dispersion containing 5 wt% of graphene sheets or carbon nanotubes (CNTs) and 0.01 wt% of epoxy resin or polyurethane. The chemical functional groups involved in this study include azide compounds (2-azidoethanol), alkylsilanes, hydroxyl groups, carboxyl groups, amine groups, sulfonic acid groups (--SO ₃ H), and two Diethyltriamine (DETA). These functionalized graphene sheets and CNTs were supplied by Taiwan Graphene Co. of Taipei, Taiwan. After removing the liquid medium (acetone) and curing at 150 ° C for 15 minutes, the graphene sheet and CNTs are well bonded to the plastic surface.

After this treatment, graphene- and CNT-bound plastic articles are subjected to electroless nickel or electroless copper plating. For nickel plating, the functionalized graphene- and CNT-combined article was treated in an electroless plating solution containing 1.2 M NiSO ₄ · 7H ₂ O for 15 minutes at 40 ° C. For Cu plating, the functionalized graphene- and CNT-bound plastic parts were immersed in an ammonia solution containing 0.5 M CuSO ₄ .5H ₂ O for 30 seconds, the solution having a pH of 9.5 and a temperature of 20 ° C.

Similar procedures have been performed for the metallization of other polymer parts, including carbon black-filled natural rubber, silicone rubber, chlorinated rubber, polycarbonate, ABS, polyethylene terephthalate (PET), and Chopped Kevlar fiber-filled phenolic resin.

We have observed that, in general, polymer parts can be metallized well using the functionalized graphene-mediated method of the present disclosure, even without an etching process. In all cases, the metal is well bonded to the surfaces of the polymer parts, these surfaces have an excellent matte appearance and outstanding scratch resistance. If functionalized graphene sheets are included alone or in combination with functionalized CNTs, the metallized surface is generally smoother than when functionalized CNTs are used alone in an impregnated dispersion.

Example 11 : Graphene / Conductive Additive Combined Polyether 碸 (PES) and Other Polymer Parts

The first set of several PES plastic rectangular strips each having a surface of 50 cm ² was immersed in an etching solution consisting of 4 MH ₂ SO ₄ and 3.5 M CrO ₃ at 70 ° C. for 3 minutes. Rinse the bars with water. Separately, a second set of several strips of the same size was used but not etched.

Subsequently, the plastic product was dipped into a graphene / conductive filler / binder dispersion containing 5% by weight of graphene sheets, 0.5% by weight of vapor-grown carbon nanofibers, and 0.01% by weight of epoxy resin or polyurethane. In this example, Cu nanowires and Ni-coated polyacrylonitrile nanofibers (obtained by electrospinning) were also used as conductive fillers. The chemical functional groups involved in this study include alkylsilanes, hydroxyl groups, carboxyl groups, amine groups, and diethylene triamine (DETA). These functionalized graphene sheets were supplied by Taiwan Graphene Co., Ltd. in Taipei, Taiwan. After removing the liquid medium (acetone) and curing at 150 ° C for 15 minutes, the graphene sheet bonded well to the plastic surface.

After this treatment, the graphene / conductive filler-bound plastic article is subjected to electroless nickel or electroless copper plating. For nickel plating, the bonded or covered polymer parts were treated in an electroless plating solution containing 1.2 M NiSO ₄ · 7H ₂ O for 15 minutes at 40 ° C. For Cu plating, the bonded or covered plastic parts were immersed in an ammonia solution containing 0.5 M CuSO ₄ .5 H ₂ O for 30 seconds, the solution having a pH of 9.5 and a temperature of 20 ° C.

Similar procedures were performed for the metallization of other polymer parts, including carbon black-filled SBR rubber, silicone rubber, polycarbonate, ABS, polyethylene terephthalate (PET), and chopped glass Fiber-filled phenolic resin.

We have observed that, in general, polymer parts can be metallized well using the functionalized graphene-mediated method of the present disclosure, even without an etching process. In all cases, the metal is well bonded to the surfaces of the polymer parts, these surfaces have an excellent matte appearance and outstanding scratch resistance. If graphene flakes are included alone or in combination with a conductive filler, the metallized surface is generally smoother than using a conductive filler alone in an impregnated dispersion.

This disclosure has the following unexpected advantages:

1. Even without using chromic acid or chromic sulfuric acid, strong adhesion between the deposited metal layer and the lightly etched polymer surface can be achieved via functionalized graphene sheet mediation and / or functionalized CNT mediation . These well-bonded metal layers show high temperature cycling resistance and withstand all usual temperature cycling shocks.

2. A wide variety of chemical functional groups can be attached to the edges or surfaces of mediated graphene sheets or carbon nanotubes that enable rapid metallization of polymer parts.

3. The disclosed process can be performed under very mild conditions that require only a short period of time. Optimal results can also be achieved without repeating the process steps typically required by prior art processes.

4. High-quality metal layers can be deposited on the surface of polymer parts without huge capital investment and large material consumption. In addition, the process can be controlled in a functionally safe and simple manner that ultimately affects the quality of the metal layer.

5. Unexpectedly, a wide variety of polymers, including not only plastics but also rubbers and composites, can be effectively metalized. In contrast, only a limited number of plastics can be satisfactorily metalized using prior art processes.

6. Since it is not necessary to etch the plastic surface at high temperature, energy saving can be achieved. Since mild etching conditions are required only in rare cases (for example, highly smooth ultra-high molecular weight PE surfaces), a wider range of mild etching solutions can be used; the need to use environmentally restricted chemicals is avoided.

7. The process or method of the present disclosure may involve only two steps: contacting the surface of the polymer part with the graphene dispersion (eg, a dipping step), and contacting the surface of the polymer part of the graphene / conductive filler with an electroless plating solution or Electrochemical plating bath contact (eg another rapid dipping step). In contrast, prior art processes required many steps: pretreatment, chemical etching, activation, chemical metallization, and electrolytic deposition of multiple metal layers (hence, additional steps).

10‧‧‧faucet assembly

12‧‧‧graphene dispersion bath

14‧‧‧graphene dispersion

16, 26‧‧‧ entrance

18, 28‧‧‧ export

22‧‧‧Metal plating bath

24‧‧‧plating solution

32‧‧‧ device

[Fig. 1] A flowchart showing the most commonly used process for producing graphene oxide sheets, which requires chemical oxidation / intercalation, rinsing, and high temperature expansion procedures.

[Fig. 2] Schematic diagram of graphene-mediated metallized polymer parts.

[Fig. 3] Schematic diagram of a graphene-mediated metallization system for a polymer article.

[Fig. 4] Schematic diagram of a graphene-mediated metallization system for a polymer article.

Claims (20)

A surface metallized polymer product, the polymer product comprising: a polymer component having a surface; a first component consisting of a plurality of graphene sheets and an optional conductive filler coated on the surface of the polymer component; Layer, and a second metallized layer deposited on the first layer, wherein the plurality of graphene sheets comprise a material selected from a primary graphene material having substantially 0% non-carbon elements or having 0.001% by weight To 25% by weight of a non-carbon element non-native graphene material of a single-layer or few-layer graphene sheet, wherein the non-native graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated Graphene, graphene bromide, graphene iodide, graphene hydrogenated, graphene nitride, doped graphene, chemically functionalized graphene, or a combination thereof, and wherein the plurality of graphene sheets and the conductive A filler is bonded to the surface of the polymer part with or without an adhesive resin, and the first layer has a thickness from 0.34 nm to 30 μm, wherein the surface metallized polymer article is not a bathroom or kitchen And is selected from vehicle parts, electrical appliances, electronic equipment, food packaging films or bags, protective clothing, antistatic films or bags, susceptors in microwave cooking, blankets, anti-reflective accessories, children's toys, product labels, express bags, sports cards , Greeting card, solar control window film, or stamped foil. The surface metallized polymer product according to item 1 of the patent application scope, wherein the conductive filler is selected from the group consisting of metal nanowires; carbon fibers; carbon nanofibers; carbon-coated fibers; conductive polymer fibers; SnO _2. Nanofibers or nanowires of ZnO ₂ , In ₂ O ₃ or indium tin oxide (ITO); conductive polymers not in the form of fibers; or a combination thereof. The surface metallized polymer product according to item 2 of the patent application scope, wherein the conductive polymer is selected from the group consisting of: polydiacetylene; polyacetylene (PAc); polypyrrole (PPy); poly Aniline (PAni); polythiophene (PTh); polyisothioindene (PITN); polyheteroarylene (PArV), wherein the heteroarylene group is selected from thiophene, furan or pyrrole; polyparaphenylene Phenyl (PpP); polyphthalocyanine (PPhc) and the like; and their derivatives; and combinations thereof. The surface metallized polymer article according to item 1 of the patent application scope, wherein the second layer has a thickness from 0.5 nm to 1.0 mm. The surface metallized polymer product according to item 1 of the patent application scope, wherein the first layer includes a binder resin that chemically bonds the graphene sheet and the conductive filler to the Polymer component surface. The surface metallized polymer product according to item 5 of the patent application scope, wherein the binder resin includes an ester resin, neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid, p-benzene Dicarboxylic acid, urethane resin, urethane resin, acrylic resin, urethane acrylic resin, or a combination thereof. The surface metallized polymer product according to item 5 of the scope of the patent application, wherein the binder resin comprises a curing agent and / or a coupling agent in an amount of 1 to 30 parts by weight based on 100 parts by weight of the binder resin. Agent. The surface metallized polymer product according to item 5 of the patent application scope, wherein the adhesive resin comprises a heat-curable resin, and the heat-curable resin comprises a member selected from the group consisting of diglycerol tetraglycidyl ether, dipentaerythritol Tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, or a combination of polyfunctional epoxy monomers. The surface metallized polymer article according to item 5 of the scope of the patent application, wherein the binder resin comprises a heat-curable resin, and the heat-curable resin comprises a bifunctional selected from the group consisting of Or trifunctional epoxy monomer: trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, tris Phenol triglycidyl ether, tetrahydroxyphenylethane triglycidyl ether, tetrahydroxyphenylethane tetraglycidyl ether, p-aminophenol triglycidyl ether, 1,2,6-hexanetriol triglycidyl ether , Glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxy triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerol triglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dibromoneopentaer Alcohol diglycidyl ether, hydrogenated bisphenol A diglycidyl Oleyl ether, (3,4-epoxycyclohexane) methyl-3,4-epoxycyclohexyl carboxylate, and mixtures thereof. The surface metallized polymer article according to item 5 of the patent application scope, wherein the binder resin comprises a UV radiation curable resin or varnish selected from the group consisting of acrylate and methacrylate oligomers , (Meth) acrylates (acrylates and methacrylates), polyols with (meth) acrylate functional groups and their derivatives, including ethoxylated trimethylolpropane tri (methyl) Acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri ( (Meth) acrylates, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, or neopentyl glycol di (meth) acrylate and mixtures thereof, and derived from Low molecular weight polyester resins, polyether resins, epoxy resins, polyurethane resins, alkyd resins, spiral resins, epoxy acrylates, polybutadiene resins, and polythiol-polyene resins. Acrylic Oligomer. The surface metallized polymer product according to item 1 of the patent application scope, wherein the polymer component comprises plastic, rubber, thermoplastic elastomer, polymer matrix composite material, rubber matrix composite material, or a combination thereof. The surface metallized polymer product according to item 1 of the patent application scope, wherein the polymer component comprises a thermoplastic, a thermosetting resin, an interpenetrating network, a rubber, a thermoplastic elastomer, a natural polymer, or a combination thereof. The surface metallized polymer product according to item 1 of the patent application scope, wherein the polymer part comprises a plastic selected from the group consisting of acrylonitrile-butadiene-styrene copolymer (ABS), styrene -Acrylonitrile copolymer (SAN), polycarbonate, polyamide or nylon, polystyrene, high impact polystyrene (HIPS), polyacrylate, polyethylene, polypropylene, polyacetal, polyester, Polyether, polyether fluorene, polyether ether ketone, polyfluorene, polyphenylene ether (PPO), polyvinyl chloride (PVC), polyimide, polyimide, polyurethane, polyurea, or a combination thereof. The surface metallized polymer product according to item 1 of the patent application scope, wherein the metal to be plated is selected from the group consisting of copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, alloys thereof, or combinations thereof . The surface metallized polymer article according to item 1 of the patent application scope, wherein the graphene sheet is further modified with nano-sized particles or coatings of catalytic metal having a diameter or thickness from 0.5 nm to 100 nm The catalytic metal is selected from the group consisting of cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof, and wherein the catalytic metal is chemically composed Different from the plated metal. A method for producing a surface metallized polymer article, the method comprising: (A) A graphene dispersion comprising a plurality of graphene flakes dispersed in a first liquid medium and optionally a conductive filler, the first liquid medium-based binder resin monomer or a liquid containing a solvent dissolved therein Binder monomer, oligomer or polymer; (B) entering a polymer article into a graphene deposition zone, wherein the graphene dispersion is sprayed, smeared, coated, cast, or printed to deposit the graphene sheet and an optional conductive filler into the polymer article To form graphene-coated polymer articles; and (C) moving the graphene-coated polymer article into a metallization chamber containing a plating solution therein for plating a layer of a desired metal onto the graphene-coated Polymer articles to obtain surface metallized polymer articles, and exit the surface metallized polymer articles from the metallization chamber; Wherein the plurality of graphene sheets include a single layer or a small layer selected from a primary graphene material having substantially 0% non-carbon elements or a non-primary graphene material having 0.001 to 25% by weight non-carbon elements Graphene sheet, wherein the non-native graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, graphene chloride, brominated graphene, graphene iodide, hydrogenated graphene, graphite nitride Ene, doped graphene, chemically functionalized graphene, or a combination thereof. The method as described in claim 16, further comprising operating a drying, heating or curing means to partially or completely remove said solvent from said graphene-coated polymer article and / or polymerize or cure said adhesive Agent to produce the graphene-coated polymer article, the graphene-coated polymer article comprising the plurality of graphene sheets bonded to the at least one surface of the polymer article. The method according to item 16 of the application, wherein the conductive filler is selected from the group consisting of: metal nanowires; carbon fibers; carbon nanofibers; carbon nanotubes; carbon-coated fibers; conductive polymer fibers; SnO ₂ , ZnO ₂ , In ₂ O ₃ or indium tin oxide (ITO) nanofibers or nanowires; conductive polymers not in the form of fibers; or a combination thereof. The method of claim 16, wherein the metal to be plated is selected from the group consisting of copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, an alloy thereof, or a combination thereof. The method according to item 16 of the application, wherein the first liquid medium further comprises a catalytic metal or a precursor thereof selected from the group consisting of cobalt, nickel, copper, iron, manganese, tin, zinc, lead, Bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof.