TW202041582A - Use of graphene-polymer composites to improve barrier resistance of polymers to liquid and gas permeants - Google Patents

Abstract

A packaging material comprising a graphene-reinforced polymer matrix composite (G-PMC) is disclosed. The packaging material has improved barrier resistance to gas and liquid permeants. Also disclosed is a method of improving barrier resistance of a polymer to a permeant, the method comprising forming a graphene-reinforced polymer matrix composite within the polymer. The packaging material may be used for packaging food, drug, perfume, etc. and to make various containers.

Description

Use of graphene-polymer composites to improve the barrier resistance of polymers to liquid and gas permeation

Invention field

This disclosure relates to the use of graphene-polymer composites to improve the barrier resistance of polymers to liquid and gas penetration.

Background of the invention

Polymer compositions have gradually been used in a wide range of applications where other materials such as metals have traditionally been used. The polymer possesses some desirable physical properties, is lightweight, and is inexpensive. In addition, many polymer materials can be formed into a number of different shapes and forms, and have obvious elasticity in the form they are obtained, and can be coated, dispersed, extruded and molded resin, paste, powder and the like Form use.

Plastic is a versatile material that has been used in many different aspects of our daily lives. It can be formed into a flexible film or transformed into many forms. A single-layer film can be used as a packaging material. For example, salun film is used as a food packaging material. Polypropylene (PP) stretch film is used to wrap the shipping box on the pallet. Polyethylene (PE) film can be converted into Ziploc bags. Multi-layer plastic combinations have been developed for different applications. For example, a strong film system composed of a multilayer film is transformed into a garbage bag. The oil-resistant film includes multiple layers of plastic materials, in which the inner plastic layer has high oil resistance and the outer plastic layer provides physical strength. The thick film made from the expanded foam layer and the top decorative layer can be used in cosmetic bags.

Plastic materials have different barrier properties to gases and liquids. Materials with high barrier properties to oxygen can have a very low permeation rate to the oxygen to be permeated. For example, Saron has a low oxygen permeation rate and is widely used in food packaging to extend the idle life of food. Polyethylene terephthalate (PET or PETE) has been used in soda bottles due to its low carbon dioxide permeation rate. Multi-layer containers have been developed to obtain low permeability to oxygen, moisture, fragrance oils, etc. Similarly, multilayer membranes with different properties for each layer have been used in waterproof applications, such as roofing materials and basic underground waterproofing materials.

Different plastic materials have different chemical resistance properties. Therefore, a plastic material compatible with one product may not be compatible with another product. However, even if its chemical properties are compatible with a product, it may still be unsuitable due to poor barrier properties. For example, high-density polyethylene (HDPE) is compatible with soda drinks, but it has poor barrier properties against carbon dioxide. The soda will lose gas and become a sugar water drink. On this occasion, HDPE bottles are used in many products, including shampoo, cleanser, water and so on. PP is compatible with nail polish, but it has poor barrier properties against organic solvents. As a result, the nail polish will dry up before reaching the consumer. Similarly, under sunlight or when exposed to UV, plastic materials will undergo degradation and lose their new properties over time. As a result, the durability of the product can be significantly reduced.

Due to the limitations of plastic materials described above, there is still a need for new types of materials with improved mechanical properties, durability, and resistance to gas, liquid, and UV light.

Summary of the invention

The present disclosure satisfies this need by providing a new and innovative plastic material containing graphene nanoflake (GNFs) with improved barrier properties, mechanical properties and durability.

In one aspect, the present disclosure provides a packaging material comprising graphene-reinforced polymer matrix composite (G-PMC), which has improved barrier resistance to a permeate, wherein the G-PMC comprises about 2% by weight Up to about 60% by weight of mechanically exfoliated particles selected from the group consisting of: monolayer and multilayer graphene nanoparticles less than 10 nanometers thick along the c-axis direction, 10 to 1,000 nanometers along the c-axis direction Meter-thick partially exfoliated multilayer graphene nanoparticles, graphite microparticles, and combinations of two or more thereof, wherein about 5% by weight of the particles are less than about 95% by weight along the c-axis direction and less than 10 nanometers Meter-thick single-layer graphene nanoparticle, multi-layer graphene nanoparticle less than 10 nanometers thick along the c-axis direction, and partially exfoliated multi-layer graphene nanoparticle 10 to 1,000 nanometers thick along the c-axis direction Particles or a combination of two or more.

In some embodiments, the graphene-reinforced polymer matrix composite material includes graphene in an amount of about 0.1% to about 30% by weight. In some specific examples, the graphene-reinforced polymer matrix composite material contains graphene between about 1% and about 10% by weight. In some embodiments, the graphene-reinforced polymer matrix composite material contains graphene in a range of about 5 wt% to about 50 wt%. In some embodiments, the graphene-reinforced polymer matrix composite material contains graphene in an amount of about 10% to about 30% by weight.

In some specific examples, the graphene-reinforced polymer matrix composite material comprises a thermoplastic polymer selected from the group consisting of acrylic resin, polymethyl methacrylate (PMMA), acrylonitrile, acrylonitrile Butadiene styrene (ABS) copolymer, polyarylate, polyacrylonitrile (PAN), polyamide imine (PAI), aromatic polyimide, aromatic thermoplastic polyester, liquid crystal polymer, poly Aryl ether-ketone, polycarbonate (PC), polydimethylsiloxane (PDMS), polyaryl ether ketone (PAEK), polyether ether-ketone (PEEK), polydicarboxylate ethylene naphthalene Ester (PEN), Polyetherimine (PEI), Polyetherketone (PEK), Polyethylene, Polyether Sulfate, Poly Sulfide (PSul), Polyethylene Terephthalate (PES), Polyethylene Terephthalate (PET or PETE), low density polyethylene (LDPE), high density polyethylene (HDPE), polyglycolic acid (PGA), polylactic acid (PLA), polylactic acid-glycolic acid copolymer (PLGA), polyoxymethylene plastic ( POM/acetal), polyphenylene ether, polyoxyphenylene (PPO), polysulfide phenylene (PPS), polypropylene (PP), polystyrene (PS), polypene (PSU), Polytetrafluoroethylene (PTFE/TEFLON®), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), thermoplastic elastomer, polyimide, thermoplastic polyimide, ultra-high molecular weight polyethylene (UHMWPE) ), natural or synthetic rubber, polyamide (PA), nylon, aliphatic polyamide, semi-aromatic polyamide, aromatic polyamide, polyamide-11 (nylon-11), polyamide Amine-12 (Nylon-12), Polyamide-4,6, Polyamide-6 (Nylon-6), Polyamide-6,10, Polyamide-6,12, Polyamide- 6,6 (Nylon-6,6), polyamide-6,9, polyamide (PA), and a mixture of two or more thereof.

In some specific examples, the graphene-reinforced polymer matrix composite material contains about 50% by weight of the total composite weight of particles selected from the group consisting of graphite microparticles, single-layer graphene nanoparticles, Multilayer graphene nanoparticles and combinations of two or more. In some specific examples, the particles comprise single and/or multilayer graphene nano particles that are less than 10 nanometers thick along the c-axis direction. In some specific examples, the thermoplastic polymer is intermolecularly cross-linked with the torn single and/or multilayer graphene sheet, wherein there are carbon atoms with reactive bonding sites at the tear edge of the sheet .

In another aspect, the packaging material includes a graphene-reinforced polymer matrix composite material, which is prepared by: (a) dispersing graphite particles into a molten thermoplastic polymer phase, wherein the graphite particles At least 50% by weight of the graphite in the graphite is composed of multilayer graphite crystals with a thickness of 1.0 to 1000 microns along the c-axis direction; and (b) applying a series of shear strain events to the molten polymer phase , So that the shear stress in the molten polymer phase is equal to or greater than the interlaminar shear strength (ISS) of the graphite particles, and each event, the molten polymer phase will continuously mechanically peel the graphite until the graphite series It is at least partially exfoliated to form a distribution of mono- and multi-layer graphene nanoparticles with a thickness of less than 10 nanometers along the c-axis direction in the molten polymer phase.

In some embodiments, the packaging material includes one or more layers of the graphene-reinforced polymer matrix composite material. In some embodiments, the packaging material further includes one or more layers of paper-containing materials. In some embodiments, the packaging material includes one or more layers of plastic-containing materials. In some embodiments, the packaging material includes one or more layers of metal-containing materials. In some embodiments, the packaging material includes one or more layers of foil. In some embodiments, the packaging material includes one or more layers of flexible ceramic materials.

In yet another aspect, the present disclosure provides a method for improving the barrier resistance of a polymeric material to a permeate. The method includes forming a graphene-reinforced thermoplastic polymer matrix composite in the thermoplastic polymer. The method of forming the graphene-reinforced polymer matrix composite in a polymer includes (a) dispersing graphite particles into the molten thermoplastic polymer phase of the polymer, wherein at least 50% of the graphite in the graphite particles The weight% is composed of multilayer graphite crystals with a thickness of 1.0 to 1000 microns along the c-axis direction; and (b) applying a series of shear strain events to the molten polymer phase so as to be in the molten polymer phase The shear stress is equal to or greater than the interlayer shear strength (ISS) of the graphite particles, and each event, the molten polymer phase will continuously exfoliate the graphite until the graphite is at least partially exfoliated in the molten polymer phase Form a distribution of single and multi-layer graphene nano particles less than 10 nanometers thick along the c-axis direction.

In some embodiments, a series of shear strain events are applied until at least 50% by weight of the graphite is exfoliated to form a single and multilayer graphite less than 10 nanometers thick along the c-axis in the molten polymer phase The distribution of ene nanoparticles. In some embodiments, a series of shear strain events are applied until at least 90% by weight of the graphite is exfoliated to form a single and multilayer graphite with a thickness of less than 10 nm along the c-axis in the molten polymer phase. The distribution of ene nanoparticles. In some embodiments, a series of shear strain events are applied until at least 80% by weight of the graphite is exfoliated to form a single and multilayer graphite with a thickness of less than 10 nm along the c-axis in the molten polymer phase. The distribution of ene nanoparticles. In some specific examples, a series of shear strain events are applied until at least 75% by weight of the graphite is exfoliated to form a single and multilayer graphite with a thickness of less than 10 nanometers along the c-axis in the molten polymer phase. The distribution of ene nanoparticles. In some specific examples, a series of shear strain events are applied until at least 70% by weight of the graphite is exfoliated to form a single and multilayer graphite with a thickness of less than 10 nanometers along the c-axis in the molten polymer phase. The distribution of ene nanoparticles. In some specific examples, a series of shear strain events are applied until at least 60% by weight of the graphite is exfoliated to form a single and multilayer graphite less than 10 nanometers thick along the c-axis in the molten polymer phase. The distribution of ene nanoparticles.

In some specific examples, the polymer is selected from the group consisting of acrylic resin, polymethyl methacrylate (PMMA), acrylonitrile, acrylonitrile butadiene styrene (ABS) copolymer , Polyarylate, polyacrylonitrile (PAN), polyamide imide (PAI), aromatic polyimide, aromatic thermoplastic polyester, liquid crystal polymer, polyarylether-ketone, polycarbonate (PC ), polydimethylsiloxane (PDMS), polyaryl ether ketone (PAEK), polyether-ether-ketone (PEEK), poly(ethylene naphthyl dicarboxylate) (PEN), polyether imide (PEI), Polyether Ketone (PEK), Polyethylene, Polyether Sulfate, Poly Sulfide (PSul), Polyethylene Sulfide (PES), Polyethylene Terephthalate (PET or PETE), Low Density Polyethylene (LDPE), high density polyethylene (HDPE), polyglycolic acid (PGA), polylactic acid (PLA), polylactic-glycolic acid copolymer (PLGA), polyoxymethylene plastic (POM/acetal), polystyrene Base ether, polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polypropylene (PP), polystyrene (PS), polyunion (PSU), polytetrafluoroethylene (PTFE/TEFLON®) , Polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), thermoplastic elastomer, polyimide, thermoplastic polyimide, ultra-high molecular weight polyethylene (UHMWPE), natural or synthetic rubber, polyamide (PA), nylon, aliphatic polyamide, semi-aromatic polyamide, aromatic polyamide, polyamide-11 (nylon-11), polyamide-12 (nylon-12), Polyamide-4, 6, polyamide-6 (nylon-6), polyamide-6,10, polyamide-6,12, polyamide-6,6 (nylon-6,6 ), polyamide-6,9, polyamide (PA) and a mixture of two or more thereof.

In another aspect, the present disclosure provides a packaging material formed from a polymer having improved barrier resistance to a permeate. In some embodiments, the permeate is gas or liquid. In some specific examples, the gas system is oxygen or carbon dioxide. In some specific examples, the liquid system is water, fuel, polar or non-polar solvent.

The packaging material may further include other materials, such as paper, ceramic material, foil or other metal materials. In some specific examples, the packaging material can be used to form a film. In some specific examples, the packaging material can be used to form a container. In some specific examples, the packaging material can be used to form a fuel tank. In some specific examples, the packaging material can be used to form a blister package. In some specific examples, the packaging material can be used to form blow molded articles. In some specific examples, the packaging material can be used to form a winding material. In some specific examples, the packaging material can be used to form waterproof materials (for example, ship coatings, basement waterproof materials, foundation waterproof materials, subsurface waterproof materials, roof waterproof materials, underwater and swimming pool repair products, waterproof membranes) .

The foregoing summary is not intended to define every aspect of the present disclosure, and additional aspects will be described in other sections such as the following detailed description. The entire document is intended to be a related integrated disclosure, and it should be understood that it takes into account all combinations of the features described in this article, even if the combination of features is not together in the same sentence, or paragraph, or chapter in this document turn up. Other features and advantages of the present invention will be apparent from the following detailed description. However, it should be understood that although the detailed description and specific embodiments indicate specific specific examples of the present disclosure, they are only provided for clarification purposes, because those skilled in the art will clarify the spirit and spirit of the present disclosure from the detailed description. Various changes and modifications within the scope.

Detailed description of the preferred embodiment

The present disclosure provides a method for using polymer matrix composites (G-PMCs) enhanced by light weight and high performance graphene to improve the barrier resistance of polymers to liquid and gas permeation. The G-PMC can be prepared by efficiently shearing and exfoliating graphite particles with good crystallization into graphene nanoflake (GNF) in a molten thermoplastic polymer. This unique method can be applied to a wide variety of thermoplastic polymers. It uses inexpensive and mined graphite as a raw material to replace expensive graphene. The polymer with improved barrier resistance can be used to manufacture packaging materials for a variety of applications, such as packaging foods, medicines, spices, etc.; and to manufacture a variety of containers.

It is known that graphene does not allow small gases to penetrate through its plane. However, the technical problems surrounding graphene include the high cost of directly using graphene and the difficulty in incorporating graphene into polymers and achieving good particle-matrix interaction in G-PMC. The weak graphene-matrix interaction creates small gaps around the graphene particles and an unobstructed path for penetration. By initially replacing graphene with mined graphite with good crystallization, the method of the present disclosure has several advantages. First of all, it will produce new new surfaces and edges on the mechanically peeled GNFs, which will strongly interact and bond with the surrounding molten polymer. Second, a very high graphite concentration can be added to the polymer, where the graphite is subsequently exfoliated into GNFs. Significant improvements in properties occurred during this process, including mechanical properties, barrier resistance, electrical conductivity, thermal conductivity, ballistic reaction, explosive reaction, UV resistance, etc. I. Graphene-enhanced polymer matrix composites (G-PMCs) with high barrier resistance

The method of the present disclosure can achieve a high concentration of GNFs in G-PMC, wherein the GNFs have good distribution and good bonding with the polymer matrix. The distribution of GNFs in G-PMC will produce tortuous paths for small gases. For example, compared with other documented graphene-enhanced polymer matrix composites in the literature, it produces excellent barrier resistance and is resistant to a variety of permeants. Such as gas and liquid permeability is significantly reduced. The present disclosure provides a new, versatile, low-cost, and scalable method for manufacturing lightweight, high-performance G-PMCs, which can replace heavier metals in a wide range of commercial and military applications. This material replacement provides cost, weight, and operating energy reduction in certain applications. Similarly, the new materials containing G-PMC have a longer effective life due to their corrosion resistance.

This method uses mined graphite as a raw material to replace graphene. Graphite has a layered structure and contains hexagonal lattice covalent bonding of carbon atoms in the layers (graphene) and van der Waals forces between layers, as shown in FIG. 1. The interlaminar shear strength (ISS) of graphite is reported to be about 0.14 GPa. Applying a shear stress greater than ISS can exfoliate graphite into graphene or GNFs. Graphene is a single-layer graphite with a Young's modulus of 1 TPa. However, the conversion of graphite to graphene is expensive because existing methods usually involve multiple steps and typically require toxic chemicals. The challenges associated with certain existing methods include low yield and re-stacking, and many of these methods cannot be scaled to produce large amounts of defect-free graphene. Furthermore, these methods have not been able to produce significant mechanical property improvements, mostly due to weak graphene-polymer interaction and the inability to incorporate graphene into the polymer at a high weight concentration. Regarding graphene, the more complicated thing is cost. Graphene is very expensive, its grade is $600/gram, and the cost of mined graphite is about $1/lb.

In comparison, this method produces a G-PMC with uniformly distributed graphene, multiple layers of graphene, and multiple layers of graphene, and its mechanical properties are significantly increased. The use of graphite as a starting material can achieve a very high loading concentration of GNFs (35-60% by weight) in the polymer, and each newly formed graphene surface generated during mechanical peeling is brand new, which provides excellent The opportunity to bond with the matrix polymer. The overall mechanical properties increase as the degree of peeling increases (ie, long mixing times in batch methods, or multiple processing cycles in modified injection molding methods). This is used for G-PMC manufacturing, through the versatility of exfoliating graphite in situ in the molten polymer, the low-cost method can produce new high-performance materials while reducing material and processing costs, which allows the introduction of a wide range of Present and future technologies.

For example, under a nitrogen blanket, a modified injection molding machine was used and processed more than ten processing cycles to melt blend 35% by weight graphite with polyether ether ketone (PEEK) to reduce the occurrence of polymer at approximately 380°C. Degradation (35G-PEEK). Before melt processing, graphite and PEEK were dried in ovens at 400°C and 160°C to remove volatiles. After each processing cycle, some samples were set aside to mark the features and the rest were pelletized and dried at 160°C for further processing cycles. A Zeiss Sigma field emission scanning electron microscope (FESEM) was used to examine the microstructure of the cryogenic fracture surface. The micrographs revealed very intimate particle-matrix adhesion, surface crystallization of PEEK on the GNF surface, transparent GNFs, uniform GNF distribution and GNF orientation, as shown in Figures 2A, 2B and 2C. The mechanical properties of tension, bending and Izod impact are determined according to ASTM D638, D790 and D256. As the processing cycle increases or the degree of peeling increases, relative to PEEK, its modulus in tension and bending increases significantly, the stress at the tension drop increases, and the notched Izod impact resistance increases, as shown in Figure 3.

There is a noteworthy increase in the tension of PEEK and 35G-PEEK, from 4 GPa to 20 GPa. This significant increase in modulus is attributable to good planar adhesion bonding and edge covalent bonding between GNFs and the polymer matrix. The impact resistance is also significantly increased. For PEEK and 35G-PEEK, it varies from 91 joules/meter to 250-450 joules/meter depending on the degree of GNF peeling. With the addition of GNFs to PEEK, its impact resistance increases, and this is attributed to the fact that GNFs has penetrated the G-PMC to create a tortuous path for crack propagation, because the crack must be well bonded to the matrix around the Distributed GNFs travel. Other findings that reduce impact resistance with the addition of graphene are most likely due to the weak graphene-matrix interface.

Comparing 35G-PEEK with 30% by weight carbon fiber reinforced PEEK indicates equal modulus (20 GPa), excellent impact resistance and lower cost. Carbon fiber costs about $20/lb, while graphite costs about $1/lb. Therefore, 35G-PEEK is ready to replace carbon fiber reinforced PEEK because of its lower cost and better impact performance.

The method of the present disclosure can be applied to a wide variety of thermoplastic polymers and support good particle-matrix interactions to produce improved mechanical properties, as shown in FIG. 4. Use the same method to peel 35 wt% graphite in high-density polyethylene, polyamide 6/6, polystyrene, polysulfide, and polysulfide phenylene to produce 35G-HDPE, 35G-PA66, and 35G-PS , 35G-PSU and 35G-PPS, which caused a significant increase in modulus and proved the feasibility of the processing method for multiple polymer matrices.

Figure 5 shows the potential modulus of G-PMCs, as indicated by the light gray arrow in the graph drawn from modulus to density. Research the similar processing method of compound double/triple graphene and PEEK. Using graphene as a starting material, only a moderate increase in torsional modulus occurs. For this reason, graphite extracted by shearing and exfoliation in situ in the molten thermoplastic polymer is used to improve mechanical properties.

This method provides these G-PMCs with improved barrier resistance, which are used for packaging users to improve the resistance to small gases (for example, oxygen, carbon dioxide and water vapor), for fuel tank users to improve the fuel and for waterproof applications ( For example, ship coatings, basement waterproofing materials, foundation waterproofing materials, below-ground waterproofing materials, roof waterproofing materials, underwater and swimming pool repair products, waterproof membranes) improve water resistance.

It is known that graphene does not allow small gases to penetrate its plane. In G-PMC, graphene must be compatible with the surrounding polymer (ie, strong particle-matrix interaction) to provide reduced permeability. The weak graphene-matrix interaction creates small gaps around the graphene particles and a path for easy penetration. However, it is well known in the art that it is difficult to achieve good graphene-polymer bonding, which limits the improvement of the mechanical properties of G-PMCs enhanced by graphene.

In the G-PMC provided by this method, GNFs are well distributed and bonded well with the polymer matrix to produce a tortuous path for the penetration of small gases, as shown in Figure 6, similar to the previously mentioned impact test period The crack propagation. Therefore, as compared with other documented graphene-enhanced PMCs in the literature, the G-PMCs described in this disclosure can achieve a more significant reduction in the permeability of small gases and fuels (ie, Excellent barrier resistance).

The G-PMC provided by this method may include unexfoliated graphite. Like graphene, graphite is also impermeable to gases and liquids. This G-PMC, which includes both graphene and graphite, represents a new type of material that can be used in packaging and other fields. Plastic materials have a wide range of applications due to their flexibility in forming various shapes. For example, plastic materials can be easily molded into films, bottles, jars, tubes, cartons, packaging materials, cardboard boxes, and thermoforms. Although it is versatile, its inherent permeability to gas and vapor limits its application, for example, in packaging. In addition, many plastic materials are sensitive to UV light that causes degradation of the plastic materials. On the other hand, metal and glass do not have this defect in the permeability to gas and vapor. However, they cannot be manufactured as easily as plastic materials. In addition, glass materials are sensitive to impact and collision forces and require additional care in shipping and handling. The G-PMC provided by this method maintains the versatility of plastic materials and has barrier resistance to gases and liquids. G-PMC also provides some degree of protection against UV light so that it can extend the idle life of the packaged product. These properties provide G-PMC as a desired material for a wide variety of applications.

In one aspect, the present disclosure provides a packaging material including graphene-reinforced polymer matrix composite material. In some specific examples, the graphene-reinforced polymer matrix composite includes graphene between about 0.1% by weight and about 50% by weight, graphene between about 0.1% by weight and about 30% by weight, and about 1% to about 10% by weight of graphene, about 5% to about 50% by weight of graphene, or about 10% to about 30% by weight of graphene.

In some specific examples, the graphene-reinforced polymer matrix composite material comprises a thermoplastic polymer selected from the group consisting of acrylic resin, polymethyl methacrylate (PMMA), acrylonitrile, acrylonitrile Butadiene styrene (ABS) copolymer, polyarylate, polyacrylonitrile (PAN), polyamide imine (PAI), aromatic polyimide, aromatic thermoplastic polyester, liquid crystal polymer, poly Aryl ether-ketone, polycarbonate (PC), polydimethylsiloxane (PDMS), polyaryl ether ketone (PAEK), polyether ether-ketone (PEEK), polydicarboxylate ethylene naphthalene Ester (PEN), Polyetherimine (PEI), Polyetherketone (PEK), Polyethylene, Polyether Sulfate, Poly Sulfide (PSul), Polyethylene Sulfide (PES), Polyethylene Terephthalate (PET or PETE), low density polyethylene (LDPE), high density polyethylene (HDPE), polyglycolic acid (PGA), polylactic acid (PLA), polylactic acid-glycolic acid copolymer (PLGA), polyoxymethylene plastic ( POM/acetal), polyphenylene ether, polyoxyphenylene (PPO), polysulfide phenylene (PPS), polypropylene (PP), polystyrene (PS), polypene (PSU), Polytetrafluoroethylene (PTFE/TEFLON®), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), thermoplastic elastomer, polyimide, thermoplastic polyimide, ultra-high molecular weight polyethylene (UHMWPE) ), natural or synthetic rubber, polyamide (PA), nylon, aliphatic polyamide, semi-aromatic polyamide, aromatic polyamide, polyamide-11 (nylon-11), polyamide Amine-12 (Nylon-12), Polyamide-4,6, Polyamide-6 (Nylon-6), Polyamide-6,10, Polyamide-6,12, Polyamide- 6,6 (Nylon-6,6), polyamide-6,9, polyamide (PA), and a mixture of two or more thereof. When the thermoplastic host polymer and the cross-linked polymer are of the same polymer species, the cross-linked polymer particles are basically a concentrated masterbatch to the extent of the cross-linked species that is intended to be introduced into the polymer formulation.

In some specific examples, the thermoplastic host polymer is selected from the group consisting of polyamides, polystyrenes, polyphenylene sulfide, high-density polyethylene, acrylonitrile butadiene styrene (ABS) polymers, polyacrylonitrile, polylactic acid (PLA), polyglycolic acid (PGA) and polylactic acid-glycolic acid copolymer (PLGA). The polyamides include aliphatic polyamides, semi-aromatic polyamides, and aromatic polyamides. The aliphatic polyamide includes non-aromatic parts. In a specific example, the aliphatic polyamide is selected from the group consisting of: polyamide-6,6 (nylon-6,6), polyamide-6 (nylon-6) , Polyamide-6,9, Polyamide-6,10, Polyamide-6,12, Polyamide-4,6, Polyamide-11 (Nylon-11), Polyamide-12 (Nylon-12) and other nylon. Nylon is a kind of aliphatic polyamides well known to be derived from aliphatic diamines and aliphatic diacids. Optionally, other polyamides that are also classified as nylon are derived from the ring-opening polymerization of lactamines, such as nylon-6 (PA-6, polycaprolactam) derived from caprolactam. In a particularly preferred embodiment, the aliphatic polyamide is polyamide-6,6, which is derived from diamine and adipic acid. The semi-aromatic polyamide includes a mixture of aliphatic and aromatic parts and can be derived from, for example, aliphatic diamines and aromatic diacids. The semi-aromatic polyamide can be a polyphthalamide (PPA) such as PA-6T, which is derived from diamine and terephthalic acid. Aromatic polyamides are also known as polyaramides, which include aromatic moieties and can be derived from, for example, aromatic diamines and aromatic diacids. The aromatic polyamide may be a p-aromatic polyamide, such as those derived from p-phenylenediamine and terephthalic acid. Typical examples of the latter include KEVLAR®.

In some embodiments, the thermoplastic host polymer is an aromatic polymer. As defined herein, the term "aromatic polymer" refers to a polymer containing an aromatic moiety as part of the polymer backbone or as a substituent attached to the polymer backbone, wherein the attachment selectivity is through a linker . The linker includes linear or branched alkylene, such as methylene, ethylene and propylene; linear or branched heteroalkylene, such as -OCH ₂ -, -CH ₂ O-, -OCH ₂ CH ₂ -, -CH ₂ CH ₂ O-, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ OCH ₂ -, -OCH(CH ₃ )-, -SCH ₂ -, -CH ₂ S-, -NRCH ₂ -, -CH ₂ NR- and similar groups, wherein the heteroatom is selected from the group consisting of oxygen, nitrogen and sulfur, and R is selected from hydrogen and lower alkyl. The linker can also be a heteroatom, such as -O-, -NR- and -S-. When the linker includes sulfur, the sulfur atom is selectively oxidized. The aromatic moiety is selected from a single ring, such as phenyl; and a polycyclic moiety, such as indol naphthyl, anthracene, etc., and optionally substituted by the following: amino, NHR, NR ₂ , halogen, nitro Group, cyano group, alkylthio group, alkoxy group, alkyl group, haloalkyl group, CO ₂ R wherein R is as defined above, and a combination of two or more thereof. The aromatic moiety may also be a heteroaryl group, which contains one to three heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur and is optionally substituted as described above. The aromatic polymer preferably contains a phenyl group as a part of the polymer backbone or as a substituent on the backbone, the latter being selectively carried out via a linker as disclosed above, wherein the phenyl group is selectively substituted as disclosed above . In some specific examples, the optionally substituted phenyl group is included in the polymer backbone such as an optionally substituted phenylene. In some other specific examples, the optionally substituted phenyl group is a substituent on the polymer backbone and is selectively connected via a linker as described above.

In some specific examples, the graphene-reinforced polymer matrix composite material contains about 50% by weight of the total composite weight of particles selected from the group consisting of graphite microparticles, single-layer graphene nanoparticles, Multilayer graphene nanoparticles and combinations of two or more. In some specific examples, the particles comprise single and/or multilayer graphene nano particles that are less than 10 nanometers thick along the c-axis direction.

In some specific examples, the thermoplastic polymer is intermolecularly cross-linked by torn single and/or multilayer graphene flakes, wherein there are carbon atoms with reactive bonding sites at the torn edges of the flakes . II. Packaging materials improved by G-PMCs and their uses

In another aspect, the packaging material includes a graphene-reinforced polymer matrix composite material, which is prepared by:

(a) Dispersing graphite particles into a molten thermoplastic polymer phase, wherein at least 50% by weight of the graphite in the graphite particles is composed of multilayer graphite crystals with a thickness of 1.0 to 1000 microns along the c-axis direction; and

(b) Apply a series of shear strain events to the molten polymer phase so that the shear stress in the molten polymer phase is equal to or greater than the interlaminar shear strength (ISS) of the graphite particles, and each event, the The molten polymer phase will continuously exfoliate the graphite until the graphite is at least partially exfoliated to form a distribution of single and multilayer graphene nanoparticles with a thickness of less than 10 nanometers along the c-axis direction in the molten polymer phase .

In some specific examples, the packaging material includes one or more layers of graphene-reinforced polymer matrix composite (G-PMC). Figure 7A illustrates an example of a packaging material containing a single layer of G-PMC, in which GNPs have been substantially uniformly distributed in the thermoplastic polymer. The graphene layer in the polymer matrix can produce a tortuous path, which acts as a gas or liquid barrier structure. High tortuosity results in higher barrier properties and lower permeability of G-PMCs.

In this method, exfoliating graphite into the molten thermoplastic polymer phase can produce varying degrees of graphene concentration in G-PMCs. In this connection, G-PMCs with low graphene concentration may have lower barrier resistance than G-PMCs with high graphene concentration. In some specific examples, as shown in FIG. 7B, the packaging material may include one or more layers of G-PMCs with a low graphene concentration and one or more layers of G-PMCs with a high graphene concentration. This configuration will ensure that the barrier resistance will not be compromised by the low tortuosity of the G-PMC layer with low graphene concentration, and that the packaging material as a whole has high barrier resistance to UV light, gas and liquid.

Figure 8A illustrates an embodiment of a packaging material with a three-layer configuration, which has one or more layers of G-PMC and one or more layers of other materials. In a specific example, the packaging material has plastic material as layer 1, G-PMC as layer 2, and plastic material as layer 3. One application of this configuration is food packaging, where the plastic layer 1 can be used to print product information or for decorative purposes; the G-PMC layer 2 provides barrier resistance to moisture, oxygen, etc.; and the plastic layer 3 can be provided and packaged Direct contact with food or any product in it. In another specific example, the packaging material has G-PMC as layer 1, plastic material as layer 2, and G-PMC as layer 3. This configuration can be useful for packaging products that require better barrier resistance to multiple permeants. In another specific example, the packaging material has plastic material as layer 1, G-PMC as layer 2, and paper as layer 3. However, it should be understood that any additional material layers can be further included between the existing layers as described in the above configuration. For example, in some specific examples, an adhesive may be used between the G-PMC layer and the plastic layer or any two adjacent layers of the packaging material. Optionally, the packaging material may have a five-layer configuration, as illustrated in Figure 8B. For example, in a specific example, the packaging material includes plastic material as layer 1, G-PMC as layer 2, plastic material as layer 3, aluminum foil as layer 4, and plastic material as layer 5. In another specific example, the packaging material includes plastic material as layer 1, G-PMC as layer 2, plastic material as layer 3, flexible ceramic material as layer 4, and plastic material as layer 5. The plastic material layer 1 can be used to directly contact the food or other products packaged therein. The plastic material layer 3 can be an adhesive for attaching the aluminum foil layer to the G-PMC layer. The plastic material layer 5 can be used to print product information and/or for decorative purposes.

In some embodiments, the packaging material further includes one or more layers of paper-containing materials. In some embodiments, the packaging material includes one or more layers of plastic-containing materials. In some embodiments, the packaging material includes one or more layers of metal-containing materials. In some embodiments, the packaging material includes one or more layers of foil. In some embodiments, the packaging material includes one or more layers of flexible ceramic materials.

In another aspect, the present disclosure provides a method for improving the barrier resistance of polymeric materials to permeates. The method includes forming a graphene-reinforced polymer matrix composite in the polymer. In some specific examples, the method of forming a graphene-reinforced polymer matrix composite in a polymer includes:

(a) Spreading graphite particles into a molten thermoplastic polymer phase polymer, wherein at least 50% by weight of the graphite in the graphite particles is composed of multilayer graphite crystals with a thickness of 1.0 to 1000 microns along the c-axis direction ;and

(b) Apply a series of shear strain events to the molten polymer phase so that the shear stress in the molten polymer phase is equal to or greater than the interlaminar shear strength (ISS) of the graphite particles, and each event, the The molten polymer phase will continuously exfoliate the graphite until the graphite is at least partially exfoliated to form a single and multilayer graphene nanoparticle with a thickness of less than 10 nm along the c-axis direction in the molten polymer phase. distributed.

In another aspect, the present disclosure provides a method for improving the barrier resistance of polymeric materials to permeates. The method includes forming a carbon fiber reinforced polymer matrix composite. In some embodiments, the method includes (a) dispersing carbon fibers into a molten carbon-containing polymer phase containing one or more molten carbon-containing polymers; (b) in the presence of the molten thermoplastic polymer phase , Breaking or cutting the carbon fiber by: (i) applying a series of shearing events to the molten polymer phase so that the molten polymer phase breaks the carbon fiber, or (ii) during the molten polymer phase The carbon fiber is mechanically broken or cut in the presence of the phase, thereby producing reactive edges on the fiber that react with and crosslink the one or more carbon-containing polymers; and (c) completely mix the broken or cut carbon fiber Phase with the molten polymer.

In some embodiments, a series of shear strain events are applied until at least 50% by weight of the graphite is exfoliated to form a single and multilayer graphite less than 10 nanometers thick along the c-axis in the molten polymer phase. The distribution of ene nanoparticles. In some embodiments, a series of shear strain events are applied until at least 90% of the graphite, up to at least 80%, up to at least 75%, up to at least 70%, or up to at least 60% by weight is exfoliated in the molten polymer A distribution of single and multi-layer graphene nano-particles with a thickness of less than 10 nanometers along the c-axis is formed in the phase.

In another aspect, the present disclosure provides a packaging material formed of a polymer obtained from the method, which improves the barrier resistance of the polymer to permeates. In some specific examples, the permeate is gas, water vapor, vapor, liquid, or liquefied gas.

Non-limiting examples of the gas include elemental gas, pure and/or mixed gas, and toxic gas. Non-limiting examples include hydrogen, nitrogen, oxygen, fluorine, chlorine, helium, neon, argon, krypton, xenon, and radon. Non-limiting examples of the pure and/or mixed gas include acetylene, air, ammonia, arsine, benzene, boron trifluoride, butadiene-1,3, butane, 1-butene, carbon dioxide, carbon monoxide, Diborane, ethane, ethylene, ethylene oxide, germane, halocarbon-14, halocarbon-21, halocarbon-22, halocarbon-23, halocarbon-32, halocarbon-116, halocarbon- 134a, halocarbon-218, halocarbon-c318, hexane, hydrogen bromide, hydrogen chloride, hydrogen sulfide, isobutane, isobutene, methane, methanol, methyl chloride, nitrogen oxide, nitrogen dioxide, nitrogen trifluoride, one Nitrous oxide, pentane, phosphine, propane, propylene, silane, silicon tetrachloride, sulfur dioxide, sulfur hexafluoride, trichlorosilane, tungsten hexafluoride, vinyl chloride. Non-limiting examples of the toxic gas include arsenic, arsine, bis(trifluoromethyl), boron tribromide, boron trichloride, boron trifluoride, bromine, bromine chloride, methyl bromide, carbon monoxide, chlorine, Chlorine pentafluoride, chlorine trifluoride, chlorofluorocarbon, chloropicrin, cyanogen, cyanogen chloride, diazomethane, diborane, dichloroacetylene, dichlorosilane, formaldehyde, germane, hexaethyl tetraphosphate , Hydrogen azide, hydrogen cyanide, hydrogen selenide, hydrogen sulfide, hydrogen telluride, nickel tetracarbonyl, nitrogen dioxide, osmium tetroxide, oxygen difluoride, fluorinated perchlorohydrin, perfluoroisobutylene, light Gas, phosphine, phosphorus pentafluoride, selenium hexafluoride, silicon tetrachloride, silicon tetrafluoride, sulphur decafluoride, sulfur tetrafluoride, tellurium hexafluoride, tetraethyl pyrophosphate, disulfide Tetraethyl pyrophosphate, trifluoroacetyl chloride, tungsten hexafluoride. In a specific embodiment, the gas permeate is oxygen or carbon dioxide.

Non-limiting examples of the liquid include water, ethanol, milk, blood, urine, gasoline, mercury, bromine, wine, rubbing alcohol, honey, coffee, and other organic or inorganic solvents. The liquid also includes aqueous solutions such as household bleach, other mixtures of different substances such as mineral oil and gasoline, emulsions such as vinegar sauce or mayonnaise, suspensions such as blood, and colloids such as paint and milk. In some specific examples, the gas is also liquefied, such as liquid oxygen, liquid nitrogen, liquid hydrogen, and liquid helium. In certain embodiments, the liquid permeate is water or fuel.

In another aspect, the packaging material may further include other materials, such as paper, ceramic materials, foils or other metal materials. In some embodiments, the packaging material may include one or more layers of polymers obtained from the method to improve the barrier resistance of the polymers to permeates. In some embodiments, the packaging material may include one or more layers of other materials.

Non-limiting examples of other materials that can be included in the packaging material include adhesives, aluminum foil, biaxially stretched polyester (bopet), container compression testing, bubble packaging materials, Bubble Wrap (trademark), Cyrus, Coated paper, corrugated fiberboard, corrugated plastic, cushion material, ethylene vinyl alcohol, expanded polyethylene, fiber tape, foam peanut, short-term glue, glass , Burlap, hot melt adhesive, inflatable air cushion, jute, kraft paper, linear low density polyethylene, liquid packaging board, low density polyethylene, medium density polyethylene, metallized film, molded pulp, mycobond, nalgene, non-woven fabric, paper, cardboard, plastic film, plastic wrap, plastic coated paper, polybutylene succinate, polyester, polyethylene, polymethylpentene, polypropylene, polypropylene Raffia fiber, polystyrene, pressure-sensitive tape, viscous polysaccharide, sarron (plastic), shrink packaging material, six-piece loop, smart label, smithers-oasis, soilon, stone pper, leather cord , Wheat straw, styrene-acrylonitrile resin, susceptor, tear strip, toilet paper, unica (material), velostat, waxtite, wikicell, wrapping tissue.

In some specific examples, the packaging material can be used to form a film. In some specific examples, the packaging material can be used to form a container. In some specific examples, the packaging material can be used to form a fuel tank (ie, automobile fuel tank, aircraft fuel tank, boat fuel tank). In some specific examples, the packaging material can be used to form a racing fuel cell. In some specific examples, the packaging material can be used to form a blister package. In some specific examples, the packaging material can be used to form waterproof materials (for example, ship coatings, basement waterproof materials, foundation waterproof materials, subsurface waterproof materials, roof waterproof materials, underwater and swimming pool repair products, waterproof membranes) .

As understood by those skilled in the art, once the packaging material has been prepared using the method of the present invention, the packaging material provided in this disclosure can be used by other methods known in the art to make any type of container. Non-limiting examples of the container include bags, boxes, bottles, boxes, blister packs, buckets, cans, cardboard boxes, coolers, crates, cups, rollers, envelopes, hoppers, trays, pots, reels , School bags, shipping containers, shrink packaging materials, storage tanks and cylinders, tubes, small glass bottles, packaging materials, etc.

Common polymers used in packaging applications include polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC) and polyethylene terephthalate (PET). The gas permeability of these polymers determines their service performance. Incorporating this packaging material will provide excellent service performance. The most common plastic packaging is HDPE rigid containers used in beverages, household products and medical items, and PET rigid containers used in carbon dioxide-containing beverages.

In some specific examples, the packaging material can be used for medicine packaging (or medicine packaging) to reduce oxygen or moisture permeability. The medical packaging is used for packaging and packaging methods of pharmaceutical preparations. It includes everything from manufacturing operations and distribution channels to end consumers. The medical packaging is highly regulated, but there will be some changes in details depending on the country or region of origin. Some common factors may include: ensuring the safety of patients, ensuring the effectiveness of the drug through the intended idle life, the consistency of the drug through different manufacturing batches, the complete documentation of all materials and processes, and the control of packaging components that may drift into the drug; Drugs are controlled by the degradation of oxygen, moisture, heat, light, etc.; prevent microbial contamination, sterility, etc. A wide variety of medical solids, liquids and gases are packaged in a wide variety of packages. Most of the common main packages are rigid containers, such as blister packages, bottles and timed medication packs. Blister packaging is used for pre-formed plastic/paper/foil packaging of formed solid medicines. The main component of the blister package is a cavity or pocket made of self-thermoforming plastic. Blister packaging typically has multiple layers of PVC, polyvinylidene chloride (PVDC), HDPE and aluminum. It usually has a cardboard backing, or aluminum foil or plastic film for sealing. Blister packaging is useful for protecting drugs against external factors such as humidity and pollutants for an extended period of time. Bottles are usually used for liquid medicines and formed tablets and capsules. Glass is most commonly used for liquids because of its inertness and excellent barrier properties. Various types of plastic bottles are used by both drug manufacturers and pharmacists in the pharmaceutical industry.

The packaging material with improved barrier resistance of the present disclosure reduces the permeability of oxygen or moisture, thereby reducing drug degradation and prolonging the idle life of the drug. This allows for thinner packaging, lower layer requirements, the need to remove the aluminum layer, simpler manufacturing, lower cost, and extended drug expiration dates. In some specific examples, the packaging material can be used to form a bottle for pharmaceutical packaging. The bottle wall can have single or multiple layers of G-PMC, and additionally and/or optionally, have one or more other plastic inner or outer layers.

Figure 9A illustrates an embodiment of a blister package made from the packaging material of the present disclosure. In some specific examples, the blister package includes an outer layer that includes a plastic material. In some embodiments, the blister package includes an intermediate layer that includes paper. In some specific examples, the blister package includes a blister cover that includes G-PMC.

Figure 9B illustrates an embodiment of a bottle including G-PMC. In some specific examples, the bottle wall may have one or more layers of different materials in order to take advantage of their respective properties. For example, in a specific example, the bottle wall includes an inner layer in contact with the product packaged therein, a center layer including G-PMC, and an outer layer. In some embodiments, the inner layer may be formed from plastic materials. In some embodiments, the outer layer can also be formed from plastic materials, and product information can be printed on it.

In some specific examples, the packaging material can be used to make a fuel tank. Common polymers used in fuel tank applications include polyamide 6 (PA6) or ethylene vinyl alcohol (EVOH), which is an adhesive layer with maleic anhydride grafted polypropylene (PP) that guarantees good adhesion Sandwiched between semi-crystalline thermoplastic layers such as high density polyethylene (HDPE). The multi-layer tank structure provides evaporative emissions exceeding current US EPA standards and excellent resistance to ethanol fuel, slush, and abrasion. However, both PA6 and EVOH are sensitive to the degree of humidity, and moisture absorption will deteriorate the barrier resistance performance. The fuel tank manufactured from this packaging material eliminates the need for this complicated layered structure, thus allowing easier manufacturing methods and reduced costs, and allowing the use of other polymer substrates not previously considered. The lightweight fuel tank made from this packaging material will also provide structural integrity, because the mechanical properties are greatly improved by GNFs, and therefore have more direct competition with the heavy steel fuel tank.

In some specific examples, the packaging material of the present disclosure can be used in waterproof applications due to its resistance to water barrier. The waterproof application has waterproof and protective coatings for all types of waterproof conditions. This packaging material is suitable for decks, outer walls, roofs, vapor/humidity barriers for intermediate boards, foundations, retaining walls, ocean-front walls, basement walls and floors, swimming pool walls, planting tanks, and thermal insulation concrete templates (Insulated Concrete Forms), floor tiles, shower trays, indoor elevated swimming pools, underwater repairs, waterfalls, tunnels, road bridges, under-mall areas in use, drinking water storage equipment, and chemical-resistant waterproofing The system provides a waterproof solution. In some specific examples, the packaging material can be used to form waterproof materials (for example, ship coatings, basement waterproof materials, foundation waterproof materials, subsurface waterproof materials, roof waterproof materials, underwater and swimming pool repair products, waterproof membranes) .

Fig. 9C illustrates an embodiment of a waterproof material including one or more layers of G-PMC. In a specific example, the waterproof material may have an inner layer, an outer layer, and a G-PMC-containing layer sandwiched therebetween. The barrier resistance of G-PMC to water provides waterproof properties to this waterproof material.

The packaging material of the present disclosure provides significant improvement in properties, including mechanical properties, barrier resistance, electrical conductivity, thermal conductivity, ballistic response, explosive response, UV light degradation resistance, and so on. The excellent mechanical properties of this packaging material reduce costs and light weight, which is particularly important for automotive, aerospace, infrastructure and military applications. In some specific examples, automobile, aircraft or aerospace parts can be formed from the packaging material.

In some specific examples, the packaging materials of the present disclosure can be used to package racing fuel cells. Racing fuel cells have a hard shell and flexible inner lining to minimize the possibility of severe damage to the vehicle in the event of a collision or other accident. The packaging material of the present disclosure provides a low-cost and light-weight solution for meeting the mechanical properties required by racing fuel cells.

In some specific examples, the packaging material can be used for food packaging. Now, most of the spices and colognes are filled in glass bottles, which will be cracked. Food packaging provides physical protection to the food; among other things, the food in the packaging may need to be protected from shock, vibration, compression, temperature, bacteria, etc. Typical food packaging may include, but is not limited to, trays, bags, boxes, cans, cardboard boxes, trays, flexible packaging, and so on. This packaging material provides excellent barrier and protects food from oxygen, water vapor, dust, UV light, etc. Penetration is a key factor in design. The packaging material has improved barrier resistance to permeation such as oxygen or water vapor to extend the idle life of food and eliminate cracking problems.

In some specific examples, the packaging material can be used for perfume packaging. In order to preserve the integrity and quality of the product packaged in the packaging container, the packaging material must be compatible with all components of the product. For example, nail polish is compatible with PP. However, PP does not have the barrier properties required to keep the solvent from penetrating through the container. Similarly, for fragrance oils and colognes, PP is compatible with fragrance and alcohol, but it does not have the barrier properties required to keep fragrance oils in the container. In comparison, the container formed from the packaging material is light in weight and can reduce the permeability of fragrance oil and/or solvent. The packaging material provides barrier resistance to oxygen and protects fragrance from oxidation. Therefore, this packaging material will possibly extend the shelf life of fragrances. The packaging material including G-PMC can provide similar properties that are useful for packaging flavors and are also required for packaging fruit wine or alcoholic beverages.

The present disclosure also provides a high-efficiency mixing method for converting a polymer composite containing good crystalline graphite particles into nano-dispersed single or multilayer graphene particles. The present disclosure additionally provides a method for in-situ and molten polymer processing to mechanically functionalize carbon fibers to generate reactive bonding sites at the fiber ends. The reactive site reacts with the polymer to chemically bond the carbon fiber to the polymer.

Information related to how to make and use the currently claimed invention is disclosed in the following published patent applications, the full contents of which are incorporated herein by reference: US 2015/0267030, US 2016/0083552 and US 2017/0218141.

The method involves exfoliating the graphite layer in situ by mixing in a batch mixer or extruder that grants repetitive high shear strain rates. In both methods, a longer mixing time provides enhanced exfoliation of graphite into graphene nanoparticles within the polymer matrix composite (PMC). In addition, additives can be used to promote sufficient graphene/polymer bonding, thereby producing low-density graphene-reinforced polymer matrix composites (G-PMC). This method can produce G-PMC at low cost, which provides many properties and advantages, including improved mechanical properties, such as increased specific rigidity and strength, increased conductivity/heat, and retained optical transparency. Furthermore, these properties can be adjusted by modifying the method, see below.

The degree of graphene exfoliation will depend on the total number of shear strain events applied to the graphite-polymer mixture. Increasing the number of shear strain events in a series will increase the degree of peeling. Therefore, depending on the number and period of in situ shear strain events, the method provides multilayer graphene, graphene flakes, graphene platelets, multiple layers of graphene, or single-layer graphene in pure and uncontaminated form. The small plate has diamond-like rigidity and is used for polymer reinforcement. Graphene in any form increases the toughness of the polymer by acting as a reinforcement for the polymer to inhibit crack propagation. Graphene can also be used as an additive to provide conductivity and heat to polymers and other compositions. The thermal conductivity of graphene makes it a desirable additive for thermal management of electronic devices and lasers.

Initially, a low degree of peeling (e.g., 10-20%) produces a significant increase in modulus at the expense of strain fracture properties. When the degree of peeling increases, the modulus continues to increase at a non-linear rate with further degradation of strain fracture properties and a slight decrease in impact energy.

As compared with pure polymer, the graphene-reinforced polymer matrix composite produced according to the present invention has at least 20% improvement in modulus, impact energy, or both. For example, as compared with the impact energy value of pure polymer, this improvement in impact energy includes an increase in impact energy value of at least 100% or an increase of at least 200%. And if compared with the modulus value of pure polymer, this improvement in modulus includes an increase in modulus value of at least 30%, an increase of at least 40%, an increase of at least 50%, an increase of at least 100%, an increase of at least 200%, or an increase of at least 500% . Therefore, in addition to better impact energy absorption and significant cost reduction, the modulus value of the G-PMCs is obtained to the extent of the carbon-fiber composite.

In some specific examples, single or multi-layer graphene nanoparticles that are generated from cracking in the cement or latex paint that peel off from the polymer in situ can form nano-sized "thermoset-like" graphene nanoparticles/ Polymer molecular clusters. Each mechanically exfoliated graphene nanoparticle is preferably covalently bonded to one or more polymer chains. In turn, the polymer chain can form additional covalent bonds with the renewed and exfoliated graphene nanoparticles. These graphene nanoparticles can form more covalent bonds with additional polymers. Similarly, each polymer chain is preferably covalently bonded or adhered to one or more mechanical graphene nanoparticle. This method can result in nano-sized molecular clusters of covalently bonded graphene nanoparticles and polymers. These molecular groups have a bonding structure similar to thermosetting block polymers that are chemically bonded together with molecules.

The composite may include one or more graphene nanoparticle/polymer molecular clusters dispersed in the polymer matrix depending on the degree of crosslinking between the polymer and the mechanically exfoliated graphene nanoparticle. The size and shape of each graphene nanoparticle/polymer cluster can vary. Those graphene nanoparticle/polymer molecular clusters contribute structural rigidity and thermosetting properties to the newly formed composite.

The term "graphene" refers to the name given to a single layer of carbon atoms densely packed into a fused benzene ring structure. Graphene when used alone can refer to multilayer graphene, graphene flakes, graphene platelets, and several layers of graphene or single-layer graphene in pure and uncontaminated form.

Graphene, the starting material graphite, is composed of a layered planar structure, in which the carbon atoms in each layer are arranged in a hexagonal lattice. The plane layer system is defined as having "a" and "b" axes, and the "c" axis system is perpendicular to the plane defined by the "a" and "b" axes. The graphene particles produced by the method of the present invention have a long-width ratio, which is defined by the "a" or "b" axis distance divided by the "c" axis distance. The aspect ratio of the nanoparticle of the present invention exceeds 25:1 and the typical range is 50:1 to 1,000:1.

The graphene can be manufactured into a graphene-polymer mixture suitable for current use, such as G-PMC, which can be pelletized by a conventional method for subsequent manufacturing processing. Optionally, a higher concentration of graphite (such as, for example, 20 to 60% by weight of the total composite weight) can be used at the beginning to provide a graphene-polymer masterbatch (including graphene and residual graphite) in a concentrated form Or), it can also be pelletized and then used to add graphene to the polymer composition as a reinforcing agent. As a further alternative, the graphene can be separated from the polymer, for example by combustion or selective dissolution, to provide substantially pure graphene particles.

The graphene-reinforced polymer composite according to the present invention typically includes about 2% to about 60% by weight, or about 5% to about 55% by weight, or about 15% to about 45% by weight of the total composite weight , Or about 25% by weight to about 35% by weight, or about 30% by weight to about 35% by weight of particles selected from the group consisting of: monolayers and multilayers less than 10 nanometers thick along the c-axis direction Graphene nanoparticles, partially exfoliated multilayer graphene nanoparticles with a thickness of 10 to 1,000 nanometers along the c-axis direction, graphite microparticles, and combinations of two or more thereof; wherein about 5 wt% to about 95% by weight, about 10% by weight, at least less than about 50% by weight, or about 10% by weight to about 45% by weight, or about 15% by weight to about 40% by weight, or about 20% by weight to about 35% by weight, or about 25% by weight to about 30% by weight are single-layer graphene nanoparticles less than 10 nanometers thick along the c-axis, multilayer graphene nanoparticles less than 10 nanometers thick along the c-axis, and Partially exfoliated multi-layer graphene nanoparticle with a thickness of 10 to 1,000 nanometers in the c-axis direction or a combination of two or more thereof.

The polymer masterbatch typically includes about 20% to about 60% by weight, or about 20% to about 50% by weight of the total composite weight, particles selected from the group consisting of: less along the c-axis direction Single-layer and multi-layer graphene nanoparticles with a thickness of 10 nm, multi-layer graphene nanoparticles with a thickness of 10 to 1,000 nm in the c-axis direction, graphite particles, and combinations of two or more thereof; Wherein about 5% by weight of the particles is at least less than about 95% by weight, or about 10% by weight to about 45% by weight, or about 15% by weight to about 40% by weight, or about 20% by weight to about 35% by weight, or about 25% by weight to about 30% by weight are single-layer graphene nanoparticles less than 10 nanometers thick along the c-axis, multilayer graphene nanoparticles less than 10 nanometers thick along the c-axis, and Partially exfoliated multi-layer graphene nanoparticle with a thickness of 10 to 1,000 nanometers in the c-axis direction or a combination of two or more thereof.

The availability of graphite-rich deposits that include fairly high concentrations (for example, about 20%) of well-crystallized graphite makes the cost of raw materials low and is a practically inexhaustible source. As discussed below, the extraction of graphite particles from the mined material can be achieved in a cost-effective manner. Synthetic graphite with high purity and excellent crystallinity (for example, pyrolytic graphite) can also be used for the same purpose. However, in this case, the exfoliation method caused by batch mixing or extrusion kneading can produce a laminated composite in which the graphene nanoparticles are oriented in a relatively large area. For specific applications, this laminated composite may be better.

For the purpose of the present invention, graphite particles are defined as graphite in which at least 50% by weight of the graphite is composed of multilayer graphite crystals with a thickness ranging from 1.0 to 1000 microns along the c-axis of the lattice structure. Preferably, graphite particles in the range of 300 to 1,000 microns are used as the starting material, and more preferably, graphite particles in the range of 500 to 1,000 microns are used as the starting material. The larger the size of the graphite particles used as the starting material, the larger the graphene flakes that will be produced when they are peeled off. Expanded graphite can also be used. Expanded graphite is prepared by forcing the crystal lattice planes in natural flake graphite to be separated, thereby expanding the graphite, for example, by immersing flake graphite in an acid bath of chromic acid and then concentrated sulfuric acid. Expanded graphite suitable for use in the present invention includes expanded graphite having open edges at the level of double layers, such as MESOGRAF.

It is possible to mechanically exfoliate graphite in the polymer matrix by polymer processing technology that grants repeated high-shear strain events, so as to mechanically exfoliate the graphite particles into multi- or single-layer graphene nanoparticles in the polymer matrix.

After high-shear mixing, the graphene flakes are uniformly dispersed in the molten polymer, have random orientation, and have a high ratio of length to width. The orientation of the graphene can be achieved by many different methods. The conventional drawing, rolling, and extrusion methods can be used to align the graphene in PMC fibers, filaments, ribbons, flakes, or any other elongated shapes. The method of manufacturing and marking G-PMC features includes four main steps, including: (a) Extract crystalline graphite particles from mineral sources; (b) Incorporate the extracted graphite particles into the polymer matrix phase, and convert the graphite-containing polymer into a graphene-reinforced polymer matrix composite (G-PMC) by a high-efficiency mixing/exfoliation method; (c) Perform morphological analysis to determine the degree of mechanical exfoliation and distribution of multilayer graphene and graphene nanoparticles; and (d) Perform X-ray diffraction analysis to determine the multi-layer graphene or graphene crystal size, as a function of mechanical exfoliation.

Highly crystalline graphite can be extracted from graphite ore by a multi-step method, as described below. Crushing: Place the drilled rod of graphite ore from the mine in a vise and crush. Grinding: Then, grind the crushed graphite ore with a mortar and pestle. Size reduction: Place the ground graphite ore on a screen with a 1 mm mesh size and reduce the size. Larger pieces that do not pass through the screen can be ground with a mortar and pestle, and then passed through a 1 mm screen to reduce the size. Finally, all materials pass the 1 mm mesh size to obtain graphite ore powder. Separated by water density

Place the 1 mm size powder in a water-filled tube column and stir until a clear separation is formed between the denser solid part and the less dense part. The density of graphite (2.09-2.23 g/cm ^ 3) is closer to the density of water (1 g/cm ^ 3) than silicon (2.33 g/cm ^3). The top layer material and water are siphoned out, and then dried. The dried graphite powder is referred to as separated mineral graphite (SMG).

In commercial implementation, very large crushing and grinders are available to produce mixed powders of tonnage, from which graphite components can be separated by standard flotation methods.

Therefore, one aspect of the present invention includes a method of manufacturing G-PMC by exfoliation in situ. In this method, during batch mixing or extrusion, the polymer uniformly blended with micron-sized crystalline graphite particles is subjected to repeated mixing element processing at a temperature, where the polymer adheres to the Graphite particles. Typical polymers have a thermal viscosity (without graphite) greater than 100 cps at the mixing temperature. The mixing temperature will vary with the polymer and can range from room temperature (for polymers that melt at room temperature) to 600°C. The typical mixing temperature range will be between 180°C and 400°C.

Therefore, the effect of each mixing pass is to shear out the graphene layer at a time, so that the original graphite particles are gradually transformed into a very large number of graphene nanoparticles. After an appropriate number of such passes, the final result is that individual graphene nano particles are uniformly dispersed in the polymer matrix phase. A longer mixing time or a higher number of passes through the mixing element provide a smaller graphite crystal size within the polymer matrix and increase the exfoliation of graphite into graphene nanoparticles; however, the shear event should not be sustained, which will Will degrade polymers.

Because the content of graphene nanoparticles increases during multiple passes through extrusion, the viscosity of the polymer matrix increases due to the growth of the number of polymer/graphene interfaces. In order to ensure the continuous refinement of the composite structure, the extrusion parameters are adjusted to compensate for the higher viscosity of the composite.

An automated extrusion system is available to allow the composite to receive as many passes as desired, where the mixing element is as described in U.S. Patent No. 6,962,431 and equipped with a recirculating air flow to direct the flow back to the extrusion The input port of the compressor. Because the processing of the graphene-reinforced PMC is straightforward and includes untreated graphene particles, its manufacturing cost is low.

In order to mechanically exfoliate graphite into multilayer graphene and/or single-layer graphene, the shear strain rate generated in the polymer during processing must cause a critical stress or interlayer in the graphite particles greater than that required to separate two layers of graphite. Shear stress of shear strength (ISS). The shear strain rate in the polymer is controlled by the polymer type and processing parameters, including the geometry of the mixer, the processing temperature, and the rotation speed per minute (rpm).

Therefore, one aspect of the present invention relates to a graphene-reinforced polymer matrix composite material, which comprises a polymer matrix composite material that is substantially uniformly distributed in the thermoplastic polymer matrix and is about 2% to about 60% by weight of the total composite weight. , Or about 5 wt% to about 55 wt%, or about 15 wt% to about 45 wt%, or about 25 wt% to about 35 wt%, or about 30 wt% to about 35 wt%, selected from The group of particles: single-layer and multi-layer graphene nanoparticles less than 10 nanometers thick along the c-axis direction, and partially exfoliated multi-layer graphene nano particles with a thickness of 10 to 1,000 nanometers along the c-axis direction , Graphite particles and a combination of two or more thereof; wherein about 5% by weight to about 95% by weight, or about 10% by weight of the particles are at least less than about 50% by weight, or about 10% by weight to about 45% by weight , Or about 15% by weight to about 40% by weight, or about 20% by weight to about 35% by weight, or about 25% by weight to about 30% by weight, is a single-layer graphene less than 10 nanometers thick along the c-axis direction Nanoparticles, multilayer graphene nanoparticles with a thickness of less than 10 nm along the c-axis direction, partially exfoliated multilayer graphene nanoparticles with a thickness of 10 to 1,000 nm along the c-axis direction, or two or more A combination of species.

According to a specific example, the graphene-reinforced polymer matrix composite material includes a substantially uniformly distributed thermoplastic polymer matrix and is about 2% to about 10% by weight, or about 2% to about 2% by weight of the total composite weight. About 9 wt%, or about 3 wt% to about 8 wt%, or about 4 wt% to about 7 wt%, or about 5 wt% to about 6 wt%, or about 8.9 wt% to about 10 wt% Particles from the following groups: single-layer and multilayer graphene nanoparticles less than 10 nanometers thick along the c-axis direction, and partially exfoliated multi-layer graphite along the c-axis direction 10 to 1,000 nanometers thick Ene nano particles, graphite particles, and combinations of two or more thereof; wherein about 5 wt% to about 95 wt%, or about 10 wt% of the particles are at least less than about 50 wt%, or about 10 wt% to about 45% by weight, or about 15% by weight to about 40% by weight, or about 20% by weight to about 35% by weight, or about 25% by weight to about 30% by weight, is a monolith with a thickness of less than 10 nanometers along the c-axis direction Layered graphene nanoparticle, multi-layer graphene nanoparticle less than 10 nanometers thick along the c-axis direction, partially exfoliated multi-layer graphene nanoparticle with a thickness of 10 to 1,000 nanometers along the c-axis direction, or two Or more combinations.

In a specific example of the graphene-reinforced polymer matrix composite disclosed above, the graphite can be doped with other elements to modify the surface chemistry of the exfoliated graphene nanoparticles. The graphite can be expanded graphite. Particularly and preferably, the surface chemistry or nanostructure of the dispersed graphite can be modified to bond with the polymer matrix to increase the strength and rigidity of the graphene-reinforced composite. In a specific example, the directional arrangement of the graphene nanoparticles is used to obtain one, two or three-dimensional reinforcement of the polymer matrix phase. In a specific example, the polymer chain is intermolecularly cross-linked by carbon atoms of the single or multilayer graphene sheet having reactive bonding sites on the edge of the sheet.

The graphene-reinforced polymer matrix composite material may further include at least one additive selected from the group consisting of fillers, dyes, pigments, mold release agents, processing aids, carbon fibers, compounds for improving electrical conductivity, and compounds for improving thermal conductivity .

Another aspect of the present invention includes automobile, aircraft, ship or aerospace parts formed from the graphene-reinforced polymer matrix composite disclosed above. In a specific example, the part is an engine part.

Yet another aspect of the present invention includes a method of preparing graphene-reinforced polymer matrix composites, such as those described herein, wherein the method includes the following steps:

(a) Disperse graphite particles into a molten thermoplastic polymer phase containing one or more of the matrix polymer; and

(b) Applying a series of shear strain events to the molten polymer phase, so that each event, the matrix polymer will continuously exfoliate the graphite until at least 10% by weight of the graphite is at least less than 50% by weight, or about 10% by weight % To about 45% by weight, or about 15% to about 40% by weight, or about 20% to about 35% by weight, or about 25% to about 30% by weight is peeled off, and in the molten polymer phase A distribution of single-layer and multi-layer graphene nanoparticles with a thickness of less than 10 nanometers along the c-axis and a distribution of multi-layer graphene nanoparticles with a thickness of 10 to 1,000 nanometers along the c-axis is formed.

In a specific example, the graphite particles are obtained by crushing and grinding graphite-containing minerals to a millimeter size, reducing the millimeter-sized particles to a micron size, and extracting micron-sized graphite particles from the graphite-containing mineral. preparation. In a specific example, the graphite particles are dispersed into the molten steel using a single screw extruder with an axial fluted extensional mixing element or a spiral fluted extensional mixing element. In the polymer phase. In a specific example, the graphite-containing molten polymer phase is subjected to repeated extrusion to cause exfoliation of the graphite material and form substantially uniformly dispersed mono- and multi-layer graphene nanoparticles in the thermoplastic polymer matrix.

In another specific example, a cross-linked G-PMC is formed by a method that includes dispersing graphite particles into a molten thermoplastic polymer phase containing one or more molten thermoplastic polymers. As explained in the examples, then, a series of shear strain events are applied to the molten polymer phase, so that each event, the molten polymer phase will continuously peel the graphene until a lower level of graphene layer is reached Thickness, after this point, peeling and tearing of the peeled multilayer graphene sheet occurs and a reactive edge that will react with the thermoplastic polymer and crosslink is produced on the multilayer sheet.

Therefore, when the graphene crosses the basal plane and breaks, it will form activated graphene and provide potential sites for cross-linking the matrix or adding other chemically unstable groups for functionalization. Therefore, it is preferable to perform the crosslinking under an inert environment or a vacuum under the condition of excluding oxygen, so that the reactive edge is not oxidized or otherwise becomes non-reactive. The formation of covalent bonds between the graphene and the matrix significantly increases the strength of the composite. Polymers that crosslink when subjected to the method of the present invention include polymers that undergo ultraviolet (UV) light degradation. This includes polymers containing aromatics such as benzene rings, such as polystyrene; polymers containing tertiary carbon, such as polypropylene and the like; polymers containing backbone oxygen, such as poly(alkylene oxide) and the like Things.

In another embodiment, the crosslinked G-PMC can be ground into particles and blended with an uncrosslinked host polymer to provide a toughening agent for the host polymer. Because of the chain entanglement between the two polymer species, the uncrosslinked polymer acquires the properties of the crosslinked polymer. Therefore, the present invention also includes the cross-linked polymer in the form of microparticles of the present invention, which can be blended with other polymers to form a high-strength composite. In a specific example, the crosslinked polystyrene and polymethyl methacrylate (PMMA) particles of the present invention can be used as toughening agents for the host polymer. The composition according to the invention may comprise a host thermoplastic polymer toughened with between 1 and 75% by weight of the crosslinked polymer particles of the invention. In a specific example, the host polymer is toughened with cross-linked polymer particles between about 10 to about 50% by weight.

The present disclosure also includes a method of in situ and molten polymer processing to mechanically functionalize carbon fibers to create reactive bonding sites at the fiber ends. The reactive site reacts with the polymer to chemically bond the carbon fiber to the polymer. This can be achieved with a variety of carbon fibers, including single or multi-wall carbon nanotubes and standard micron-sized carbon fibers. It can be associated with a variety of polymers with double bonds (carbon-carbon double bonds, carbon-oxygen double bonds, etc.) or a variety of tertiary carbon bonding chemical groups. When the graphite is mechanically exfoliated into graphene from the polymer in situ, good bonds have been similarly observed at the fracture sites of the covalent bonds between graphite and graphene.

These fibers are simultaneously broken or cut in the molten polymer during melt processing, and this can be achieved by specially designed cutting tools in the melt processing equipment, or through high shear during melt processing, or by The combination of the two is complete. The new fiber ends that are opened by breaking or cutting the fiber when surrounded by liquid polymer will introduce dangling bonds (free radicals) with unfilled valences, which provide reactive sites on the fiber ends, which represent the same Polymers with the above-mentioned properties have strong bonds such as covalent bonds. The resulting solid composite has improved mechanical properties and optimal fiber length after cooling, and subsequently, the cost will be greatly reduced by this bond.

In one aspect, the present invention provides a method for converting polymer composites including carbon fibers into reactive ends or edges by mixing in a batch mixer or extruder that grants repeated high shear strain rates. High-efficiency mixing method of broken carbon fiber. This method produces CF-PMC at low cost that can provide many properties and advantages, including increased specific rigidity and strength, improved conductivity/heat, and retention of optical transparency. Furthermore, these properties can be adjusted by modifying the method, see below. In some cases, inert gas or vacuum can be used during processing. Other advantages of breaking carbon fibers in situ are the avoidance of processing carbon fibers of reduced size and the need to disperse them uniformly in the polymer matrix phase. Excellent mixing produces a finer composite structure and very good particle distribution.

The carbon fiber reinforced polymer according to the present invention typically includes about 0.1 to about 30% by weight of carbon fibers or nanotubes. More typically, the polymer includes between about 1.0 to about 10% by weight of carbon fiber or nanotube. According to a specific example, the carbon fiber reinforced polymer matrix composite includes about 1% by weight to about 10% by weight, or about 2% by weight to about 9% by weight, or about 3% by weight to about 8% by weight, or about 4% by weight. Weight% to about 7% by weight, or about 5% to about 6% by weight of carbon fibers or nanotubes (based on the total composite weight). The polymer masterbatch typically includes up to about 65% by weight of carbon fibers or nanotubes, and more typically between about 5 to about 50% by weight of carbon fibers or nanotubes. According to a specific example, the masterbatch includes about 10 to about 30% by weight of carbon fiber or nanotube.

The mechanical functionalization of carbon fibers in the polymer matrix can be achieved by granting repeated high shear strain events to mechanically break the carbon fibers in the polymer matrix. After high-shear mixing, the mechanically reduced-sized carbon fibers are uniformly dispersed in the molten polymer with random orientation and high length to width ratio.

In a specific example, graphite particles are also added to the molten polymer and mechanically exfoliated into graphene through a series of shear strain events. The size of the graphite particles is usually not greater than 1,000 microns, and the degree of exfoliation of the graphite particles can usually be 1 to 100%, resulting in a graphene to graphite weight ratio ranging from 1:99 to 100:0. This peeling method is disclosed in US 2015/0267030, and this disclosure is incorporated herein by reference in its entirety.

The amount of graphite added to the molten polymer can be the highest amount and includes the amount of carbon fibers and nanotubes added, provided that the total content of the carbon fibers, nanotubes, and graphene produced or a mixture of graphite and graphene does not More than 65% by weight. Typically, the weight ratio of the graphene or the mixture of graphite and graphene to carbon fiber and/or nanotube is in the range of 5:95 to 50:50, and more typically in the range of 25:75 to 33:67 .

It should be understood that the embodiments and specific examples described in this article are only for illustrative purposes, and those familiar with the art will suggest various modifications or changes in light of this, and they are included in the spirit and authority of this application. Within the scope of the attached patent application. III. Examples Example 1: Preparation of G-PMC material

The four materials used in these examples include flake graphite (manufactured by Asbury Carbons), polyetheretherketone (PEEK), general purpose polystyrene (PS), and low melt flow polyethylene (HDPE). PEEK has a specific gravity of 1.32, a melt mass flow rate (MFR) of 3.0 g/10 minutes at 400°C and 2.16 kg, a bending modulus of 3.8 GPa, a bending strength of 128 MPa and a tensile modulus of 4 GPa. PS has a specific gravity of 1.04, an MFR of 7.0 g/10 minutes at 200°C and 5 kg, a bending modulus of 3.1 GPa, a bending strength of 57 MPa and a tensile modulus of 3.4 GPa. HDPE has a specific gravity of 0.952, an MFR of 0.06 g/10 minutes at 190°C and 2.16 kg, a bending modulus of 1.1 GPa, a bending strength of 22 MPa and a tensile modulus of 1.2 GPa. Sample Preparation

High-shear melt processing methods are used to manufacture PEEK (50 wt% graphite/graphene, 50G-PEEK), PS (35 wt% graphite/graphene, 35G-PS) and HDPE (35 wt% graphite/graphene, 35G-HDPE) has a good distribution of high-load G-PMCs (ie, master batches). In order to determine the masterbatch properties of these high-load G-PMCs, each is diluted with the same grade of polymer to obtain G-PMCs with lower graphite/graphene load (ie, graphite/graphene with lower weight %) .

Before processing the diluted sample, dry PEEK and 50G-PEEK to remove adsorbed water, dry PS and 35G-PS to remove adsorbed water, and dry HDPE and 35G-HDPE to remove adsorbed water. Then, the components are dry blended, and the mixture is directly added to the hopper of a molding machine with a novel screw design. Then, the components are processed under nitrogen blanket and various pressures according to the substrate. A PID temperature-controlled stainless steel mold was used for the PEEK substrate composite, and an ASTM D638 type 1 tension sample with a cross-sectional dimension of approximately 3.4 mm by 12.5 mm was manufactured. The same processing method was used to make PEEK, PS and HDPE samples as controls for comparison with G-PMCs.

After processing, the graphene-reinforced polymer matrix composite material composed of 2 wt%, 5 wt%, and 10 wt% graphite/graphene in the PEEK matrix was manufactured. These complexes are referred to herein as 2G-PEEK, 5G-PEEK and 10G-PEEK, respectively. Similarly, in the PS matrix, 1.8% by weight, 4.4% by weight and 8.9% by weight of graphite/graphene in the PS matrix are also manufactured. These complexes are referred to herein as 1.8G-PS, 4.4G-PS and 8.9G-PS, respectively. And in the HDPE matrix, 1.8% by weight, 4.4% by weight and 8.9% by weight of graphite/graphene in the HDPE matrix were produced. These compounds are referred to herein as 1.8G-HDPE, 4.4G-HDPE and 8.9G-HDPE, respectively. Example 2: Features of G-PMCs

Scanning electron microscope (SEM), bending mechanical test and tensile mechanical test were used to mark the morphology and mechanical properties of the composite.

According to ASTM D790, the MTS QTest/25 Elite controller is used to mark the bending mechanical properties of the composite, which is 500 Newtons for PS and HDPE composites, and at a crosshead speed of 1.3 mm/min and 49 mm A load element of 5 kN is attached to the supporting span.

According to ASTM D638, the MTS QTest/25 Elite controller is used to mark the tensile mechanical properties of the composite, which is a 25 kN load cell at a crosshead speed of 1.41 mm/min. SEM analysis

The morphology of graphene, PEEK, 2G-PEEK and 5G-PEEK was analyzed by scanning electron microscope (SEM). SEM samples of molded samples were prepared by freeze fracture. The cracked surface was mounted on an aluminum snail, coated with gold to a thickness of 5 nm, and placed in a vacuum overnight before observation. Zeiss Sigma field emission SEM, in-lens and secondary electron detector were used to observe the dispersion/distribution of graphene in PEEK and the interaction of graphene particles and matrix. All observation systems use an accelerating voltage of 5 kiloelectron volts.

In Fig. 10, the morphology of 10G-PEEK (left) and 10G-PS (right) are shown in SEM images. A good graphite/graphene distribution can be seen in these two composites, which illustrates the successful use of high-load masterbatch to produce a uniform composite. Example 3: Processing and characteristics of CNT-reinforced nylon 66 composite

The polymer-carbon nanotube composite (PCNC) is different from the conventional carbon-fiber composite in that it has a higher interface area between the reinforcing carbon and the polymer matrix. It has been suggested that the introduction of uniformly distributed carbon nanotubes (CNTs) into the polymer matrix should produce improved properties of the mixture beyond simple general examples. The challenge is to make full use of the excellent properties of CNTs in the composite material.

Carbon nanotubes are regarded as ideal reinforcing materials for polymer matrix due to their high length to width ratio, low density, noteworthy mechanical properties and good electrical conductivity/heat. One of the substrates that has been studied is the commercially important nylon 66. However, the improvement of its properties has not been obvious so far, apparently due to poor CNT/polymer interface bonding and severe CNT agglomeration.

These obstacles have now been overcome by the use of new processing methods, including high-shear mixing in the molten polymer to cause de-agglomeration and dispersion of CNTs, and at the same time by creating new polymer chain bonding sites on the CNTs. Adhesive bonding and covalent bonding. An attempt is also made to increase impact energy absorption by forming a two-phase composite, which includes uniformly dispersing high-component strong CNT-reinforced nylon particles in a tough nylon matrix.

Carbon nanotubes (CNTs) are composed of hexagonal-bonded carbon atoms, which are rolled up to form tubes. Single-walled carbon nanotubes (SWCNT) contain a single layer of this carbon atom tubular structure. However, the structure of multi-wall carbon nanotubes (MWCNT) is still somewhat controversial. In one model, the MWCNT conjecture is that a single graphene sheet is rolled into a reel. In another model, MWCNT is considered to be made of a coaxial layer of hexagonal carbon arranged in a spiral, which matches at the junction line to result in a telescopic-shell structure. In another model, a combination of reel-shaped and telescopic-shell structure has been proposed.

It is known that the increase in elastic modulus and strength of nylon-CNT composites results from the addition of small amounts of CNTs to the polymer matrix. Although the Van der Waal bond dominates the interaction between CNTs and polymers, some CNT composites also adhere via covalent bonds, which has been shown to play a role in the reinforcement of CNT composites.

The pulling force required to remove the length provided by the individual MWCNTs embedded in the polyethylene-butene copolymer measured by AFM has been clarified that there is a covalent bond between the outer layer of the MWCNT and the polymer matrix. It also shows that the behavior of the polymer matrix near the interface is different from that of the polymer in the bulk, which is due to the CNT outer diameter having the same size as the radius of the polymer chain.

Because of the tendency of CNTs to agglomerate, the difficulty of aligning in the matrix, and the often poor load transfer, there have been some reports trying to use different polymer matrix phases to make composites.

The present invention provides notable improvements in the rigidity and strength of CNT-reinforced nylon composites, see below. The composite is characterized by increased impact energy absorption. This article provides processing parameters to achieve excellent mechanical properties and performance. Example 4: Preparation and characteristics of G-PMC film 1. Sample Preparation material (a) Mined graphite with good crystallization, high purity; and (b) HDPE. (c) G-PMCs are prepared by high shear melt mixing method.

Before melt processing, let the graphite dry in a furnace to remove volatiles. 35% by weight of dry graphite is dry blended with HDPE, and then a molding machine is used for high-shear melt processing and tensile samples are manufactured. In order to achieve a high degree of graphite exfoliation, these components are processed for more than ten processing cycles to produce 35G-HDPE masterbatch. Then, dry and blend HDPE and 35G-HDPE masterbatch and use the same high-shear melt processing method for melt processing to produce samples including 0, 1, 5, 10, 20 and 35% by weight graphite, and for each concentration Manufactured tension samples, HDPE, 1G-HDPE, 5G-HDPE, 10G-HDPE, 20G-HDPE and 35G-HDPE. 2. Film preparation

Each sample prepared in 1.2 (0, 1, 5, 10, 20, and 35% by weight graphite in HDPE) was pelletized and melt-processed using an extruder attached with an edge die to produce a film. Cut out a suitable section for subsequent penetration testing. 3. Penetration Testing

The penetration of small gases and fuels through HDPE, 1G-HDPE, 5G-HDPE, 10G-HDPE, 20G-HDPE and 35G-HDPE samples will be measured to determine the effect of GNF concentration on the permeability of HDPE, and the most The ideal concentration is used for secondary processing to arrange the GNFs in the HDPE to further reduce the penetration rate. 3.1. Small gases (oxygen, carbon dioxide and water vapor) oxygen

Mocon OX-TRAN (or similar instrument) will be used to measure oxygen permeation according to the following: ASTM D3985 standard test method, using Coulomb sensor to measure the oxygen penetration rate through plastic film and sheet; ASTM F1927 standard test method, using Coulomb The detector determines the oxygen penetration rate, permeability and permeation through the barrier material under controlled relative humidity; or similar test methods that have been well documented in the literature.

ASTM D3985 will determine the steady state rate of oxygen penetration through the G-PMC membrane and the control polymer membrane, and provide the following determinations: (1) Oxygen penetration rate (OTR), and (2) The membrane's oxygen permeability (PO2) ). The several samples of each sample reported are averaged. ASTM F1927 will determine the steady state rate of oxygen penetration through the G-PMC film and the control polymer film at the provided temperature and RH%, and provide the following determinations: (1) Oxygen penetration rate (O2GTR), (2 ) The permeability of the membrane to oxygen (PO2), and (3) the permeability coefficient of the membrane to its thickness (P"O2). The average of several samples of each sample will be reported. carbon dioxide

The permeation of carbon dioxide will be measured on G-PMC membranes and control polymer membranes according to ISO 2556-Determination of gas penetration rate of plastic films and sheets under atmospheric pressure-Manometric method or equivalent methods. The several samples of each sample reported are averaged. water vapor

The G-PMC film and the control polymer film will be measured for water vapor permeation in accordance with the ASTM E96 Standard Test Method for Water Vapor Penetration Materials or an equivalent method. The water vapor penetration (WVT) of each sample will be reported as the average of several samples. 3.2. Fuel

Fuel infiltration will be performed according to the cup weight loss procedure (or equivalent procedure) of SAE International J2665. The cup including fuel was sealed with G-PMC film and control polymer film, and the mass loss due to diffusion was monitored every 24 hours. The cup was stored in an oven covered with a nitrogen blanket at approximately 60°C to flush away flammable vapors. The several samples of each sample reported are averaged. 4. G-PMC optimization and testing

After analyzing the penetration results, the optimal graphite concentration in HDPE and the GNFs that undergo secondary processing to be oriented in HDPE will be determined, which should further reduce penetration. A Brabender heated two-roll mixer (or equivalent) will be used to align the GNFs potentially at 90 degrees to the through surface to further reduce permeability. The aligned G-HDPE and HDPE samples will undergo penetration testing. Example 5: Mixed time effect

A homogeneous, high-shear melt mixing method is used to combine graphite and high-density polyethylene (HDPE) to exfoliate graphite into graphene nanoflake (GNFs) in HDPE to produce G-HDPE nanocomposite. Two different methods were used to determine the barrier resistance to small gases passing through these G-HDPE nanocomposite membranes. First, by adding 0.5% by weight graphite to HDPE and melt blending with different mixing times to study the effect of mixing time, including 30, 60, 90 and 120 minutes. Secondly, the effect of GNF concentration was studied by adding 0, 1, 2, 5, 10, 20, 25, 30, and 35% by weight graphite to HDPE and melting and mixing each for 90 minutes. These samples are marked as %G-HDPE. For example, 35G-HDPE refers to the exfoliation of 35 wt% graphite in HDPE to form GNFs. HDPE was processed separately under the same mixing time of 30, 60 and 90 minutes as a control. The components are processed at a temperature range of 205°C to 235°C. The extrudate was compression molded, and a film was formed under pressure at a temperature of 190°C and a pressure of 11 MPa for about 20 seconds. Remove the sample from the block and allow it to cool at room temperature while still being packaged in aluminum foil. The target film thickness is between 75-200 microns.

The mined graphite is obtained from Asbury Carbons (mills grade 3627, with purity 99.2%), and HDPE injection molding grade (melt flow rate at 190°C is 4.8 g/10 minutes) and has a melting temperature of 132 ℃. Before processing, graphite and HDPE were dried in an oven at 400°C for four hours and at 70°C for 30 minutes.

After the high shear melt mixing time (a) 30 minutes, (b) 60 minutes, (c) 90 minutes and (d) 120 minutes, the photograph of the compression molded 0.5G-HDPE film is shown in FIG. 11. The film showed uniformity without any visible GNF particles. The optical microscope images showed good GNF particle distribution in HDPE and showed that increasing the mixing time for 120 minutes would increase the uniformity of GNF particle size (Figure 12). This figure shows the GNF particle diameter in the AB plane.

At Mocon Laboratory, according to ASTM D3985, use Oxtran 2/21 oxygen permeability instrument and operate until steady state oxygen penetration is achieved to determine the oxygen penetration of 0.5G-HDPE membrane by melt mixing for 30, 60, 90 and 120 minutes . The sample was tested under a differential pressure of 760 mmHg against a carrier gas of 98% nitrogen and 2% hydrogen at a temperature of 23°C with dry oxygen. The sample area is 5 square centimeters or 20 square centimeters depending on the thickness uniformity.

The oxygen permeation results of the 0.5G-HDPE membrane are shown in Figure 13. The measured average (cubic centimeter x mm)/(2x day) oxygen will decrease with the addition of 0.5 wt% GNFs to HDPE after 60, 90 and 120 minutes of mixing, because the degree of graphite exfoliation will increase (ie, graphite particles The size decreases and increases). With only 0.5 wt% graphite added to HDPE and melt-mixed for 90 minutes to exfoliate graphite into GNFs, and compared with HDPE, the penetration is reduced by 13%, and this indicates a high degree of graphite exfoliation into GNFs and good GNF-matrix Interaction. Example 6: Effect of GNF concentration

The 35G-HDPE nanocomposite film was mixed in a uniform, high-shear molten state for 90 minutes and then compressed and molded. Using its cold fractured film surface, it was shown in Figures 14A and 14B using a field emission scanning electron microscope. As shown in Figure 14A, GNFs are well distributed in HDPE and arranged parallel to each other. In Figure 14B, good particle-matrix interaction has been demonstrated because HDPE wets the GNF surface and edges.

Using a fixed-volume device, at a temperature of 35°C, it is determined to penetrate nitrogen, oxygen, and carbon dioxide through G-HDPE membranes containing 0, 0.5, 5, 10, 20, 25, 30 and 35 wt% GNFs. Use Devcon 5-minute epoxy resin to install the membrane on a flat brass ring with an inner area of 1.68 cm² or 2.84 cm² (depending on the thickness of the membrane) and a porous metal base sealed in the device On the top. The sample was degassed overnight. During the test, vacuum is applied downstream of the sample and then isolated except for the sample interface. The test gas enters upstream at a pressure of 1-2.5 atmospheres. This pressure difference causes gas to diffuse through the sample, and using [EQ 1], the change measured at the downstream pressure is used to calculate permeability. Expose each membrane to nitrogen, oxygen, and carbon dioxide, and degas for approximately 1 hour between each exposure. During the experiment, a python script was used to record the downstream pressure in a 1-second interval. Monitor the time span required to achieve a linear pressure increase, and conduct the experiment approximately 5 times this span.

among them: V=device volume l = sample thickness A=sample area Δp = pressure difference across the sample dp/dt(exp.)=The downstream pressure change rate measured during the experiment dp/dt (leakage) = the downstream leakage rate measured by the device before the experiment

The permeation of oxygen, nitrogen, and carbon dioxide through a G-HDPE membrane containing 0, 0.5, 5, 10, 20, 25, 30, and 35 wt% GNFs and melt-mixed for 90 minutes is shown graphically as a function of GNF concentration. 14C and the table are listed in Table 1. Adding GNFs to HDPE reduces the penetration of these small gases through the G-HDPE nanocomposite membrane. For 35G-HDPE membrane, compared with HDPE membrane, the permeation of oxygen, nitrogen and carbon dioxide is reduced by 72, 75 and 76% respectively. In Figure 15, in order to facilitate the display of the permeation of each gas as a function of the GNF concentration and the most ideal axis scale, (A) carbon dioxide, (B) oxygen and (C) nitrogen. Table 1. Permeation of nitrogen, oxygen and carbon dioxide through G-HDPE nanocomposite membranes containing 0, 0.5, 5, 10, 20, 25, 30 and 35 wt% GNFs and melt-mixed for 90 minutes. Average film thickness oxygen nitrogen carbon dioxide graphite% (Μm) Penetration (barrer) change% Penetration (barrer) change% Penetration (barrer) change% 0 75 1.08 0 0.35 0 3.66 0 0.5 98 1.09 0.96 0.36 5 3.53 -3.5 5 98 1.30 20 0.33 -4 3.88 6 10 165 0.95 -12 0.39 12 2.91 -20 20 98 Not tested 0.28 -19 2.59 -29 20 132 0.64 -41 0.21 -40 1.78 -51 25 91 0.44 -59 0.22 -36 0.97 -73 30 132 0.47 -57 0.15 -55 1.51 -59 35 132 0.30 -72 0.09 -75 0.86 -76

The description of the foregoing embodiments and preferred specific examples should be used as clarification rather than as a limitation of the present invention, which is defined as the scope of the patent application. As will be readily apparent, many variations and combinations of the features proposed above can be used without departing from the invention as proposed in the patent application. This change is not deemed to depart from the spirit and scope of the present invention, and all these changes are intended to be included in the scope of the following patent applications. In order to assist in understanding the detailed description of the composition and method according to the present disclosure, several expression definitions are provided to make it easy to clearly reveal the various aspects of the present disclosure.

Unless defined in other aspects, all technical and scientific terms used in this article have the same meaning as generally understood by those who are generally familiar with the art to which this disclosure belongs. It should be noted here that when used in this patent specification and the appended scope of patent applications, unless the context clearly specifies, the singular forms "one", "one" and "the" include plural references. Unless mentioned in other aspects, the terms "including", "comprising", "containing" or "having" and their variations mean the items listed later and their Equivalents and additional themes.

Other objectives, features, and advantages of the present invention will be clarified from the following detailed description. However, it should be understood that although specific specific examples of the present invention are indicated, the detailed description and examples are only provided for illustrative purposes. An additional consideration is that changes and modifications within the spirit and scope of the present invention will be explained in detail by those familiar with the technology.

Figures 1A and 1B are diagrams of graphite, which show the layered structure of covalently bonded carbon atoms in a hexagonal array and the secondary bonding between layers (Figure 1A) and single-layer graphite graphene (Figure 1B) .

Figures 2A, 2B, and 2C (collectively referred to as "Figure 2") show the FESEM micrographs of 35G-PEEK peeled off 35 wt% GNFs in PEEK; Figure 2A shows a uniform GNF distribution; Figure 2B shows PEEK in Edge covalent bonding and surface crystallization on the edge of GNF; and Figure 2C shows transparent GNFs and very good adhesion between GNFs and PEEK matrix.

Figures 3A, 3B and 3C (collectively referred to as "Figure 3") show the mechanical properties of PEEK and 35G-PEEK, as a function of processing cycles; Figure 3A shows the tensile modulus of PEEK and 35G-PEEK, as in processing Figure 3B shows the flexural modulus of PEEK and 35G-PEEK as a function of processing cycles; and Figure 3C shows the Izod impact resistance of PEEK and 35G-PEEK as a function of processing cycles.

Figure 4 shows the G-PMC tensile modulus of PEEK, PPS, PSU, PS, PA66, and HDPE polymers and their 35% by weight exfoliated graphite in each polymer.

Figure 5 shows the modulus vs. density of polymer, thermoplastic compound, current G-PMC, voltage G-PMCs, carbon fiber epoxy compound and metal.

Figure 6 shows the tortuous diffusion path through the G-PMC.

Figures 7A and 7B (collectively referred to as "Figure 7") show examples of packaging materials. Figure 7A shows an embodiment of a packaging material containing G-PMC, and Figure 7B shows an embodiment of a packaging material containing a G-PMC layer with a low graphene concentration and a G-PMC layer with a high graphene concentration .

Figures 8A and 8B (collectively referred to as "Figure 8") show examples of laminated packaging materials. FIG. 8A shows an example of a packaging material with a three-layer configuration; and FIG. 8B shows an example of a packaging material with a five-layer configuration.

Figures 9A and 9B (collectively referred to as "Figure 9") show examples of the use of packaging materials. Figure 9A shows an example of a blister package formed from the packaging material. Figure 9B shows an example of a bottle formed from the packaging material. Figure 9C shows an example of a waterproof material formed from the packaging material.

Figure 10 shows the morphology of 10G-PEEK (left) and 10G-PS (right).

Figures 11A, 11B, 11C, and 11D (collectively referred to as "Figure 11") show photos of 0.5G-HDPE film compression molded after mixing for a period of time under high shear melting, 30 minutes (Figure 11A), 60 minutes ( Figure 11B), 90 minutes (Figure 11C) and 120 minutes (Figure 11D).

Figures 12A, 12B, 12C, and 12D (collectively referred to as "Figure 12") show the optical microscope images of a 0.5G-HDPE film compression molded after mixing for a period of time under uniform, high-shear melting, 30 minutes (Figure 12A) ), 60 minutes (Figure 12B), 90 minutes (Figure 12C) and 120 minutes (Figure 12D).

Figure 13 shows the oxygen permeation measured through the 0.5G-HDPE membrane after 30, 60, 90 and 120 minutes of mixing.

Figures 14A, 14B and 14C (collectively referred to as "Figure 14") show the preparation of GNFs by homogeneous, high-shear melt mixing of 35% graphite in HDPE for a 90-minute mixing time, followed by compression molding. SEM micrographs of 35G-HDPE nanocomposite film, scale bars 2 microns (Figure 14A) and 200 nanometers (Figure 14B). Figure 14C shows the permeation of nitrogen, oxygen, and carbon dioxide through a G-HDPE nanocomposite membrane with 0, 0.5, 5, 10, 20, 25, 30, and 35 wt% GNFs after 90 minutes of melt mixing. As a function of the GNF concentration in HDPE.

Figures 15A, 15B and 15C show that carbon dioxide (Figure 15A), oxygen (Figure 15B) and nitrogen (Figure 15C) have 0, 0.5, 5, 10, 20, 25, 30 and 35 wt% GNFs melt mixed in 90 minutes The later penetration in the HDPE nanocomposite membrane is a function of the GNF concentration.

Claims (22)

A packaging material comprising a graphene-reinforced thermoplastic polymer matrix composite material, wherein the graphene-reinforced polymer matrix composite material contains about 2% to about 60% by weight of mechanically exfoliated particles selected from the group consisting of : Single-layer and multi-layer graphene nanoparticles less than 10 nanometers thick along the c-axis direction, partially exfoliated multi-layer graphene nanoparticles 10 to 1,000 nanometers thick along the c-axis direction, graphite microparticles, and two Or more combinations, wherein about 5% to about 95% by weight of the particles are monolayer graphene nanoparticles less than 10 nanometers thick along the c-axis direction, and less than 10 nanometers along the c-axis direction Meter-thick multilayer graphene nanoparticles, partially exfoliated multilayer graphene nanoparticles with a thickness of 10 to 1,000 nm along the c-axis direction, or a combination of two or more thereof. The packaging material of claim 1, wherein the graphene-reinforced polymer matrix composite material contains between about 1% to about 50% by weight of graphene nanoparticles. The packaging material of claim 1, wherein the graphene-reinforced polymer matrix composite material contains graphene nano-particles between about 0.1% by weight and about 30% by weight. The packaging material of any one of claims 1 to 3, wherein the graphene-reinforced polymer matrix composite material comprises about 5% to about 55% of the total composite weight of particles selected from the group consisting of: Graphite particles, single-layer graphene nanoparticles, multilayer graphene nanoparticles, and combinations of two or more thereof. The packaging material according to any one of claims 1 to 4, wherein the graphene-reinforced polymer matrix composite material comprises a thermoplastic polymer selected from the group consisting of acrylic resin, polymethyl methacrylate ( PMMA), acrylonitrile, acrylonitrile butadiene styrene (ABS) copolymer, polyarylate, polyacrylonitrile (PAN), polyamide imide (PAI), aromatic polyimide, aromatic thermoplastic Polyester, liquid crystal polymer, polyarylether-ketone, polycarbonate (PC), polydimethylsiloxane (PDMS), polyaryletherketone (PAEK), polyetherether-ketone (PEEK), Polyethylene naphthyl dicarboxylate (PEN), polyether imide (PEI), polyether ketone (PEK), polyethylene, polyether sulfide, polysulfide (PSul), polyepoxyethylene (PES) , Polyethylene terephthalate (PET or PETE), low density polyethylene (LDPE), high density polyethylene (HDPE), polyglycolic acid (PGA), polylactic acid (PLA), polylactic acid-glycolic acid copolymer (PLGA), polyoxymethylene plastic (POM/acetal), polyphenylene ether, polyoxyphenylene (PPO), polyphenylene sulfide (PPS), polypropylene (PP), polystyrene (PS ), Polyurethane (PSU), Polytetrafluoroethylene (PTFE/TEFLON®), Polyvinyl Chloride (PVC), Polyvinylidene Fluoride (PVDF), Thermoplastic Elastomer, Polyimide, Thermoplastic Polyimide , Ultra-high molecular weight polyethylene (UHMWPE), natural or synthetic rubber, polyamide (PA), nylon, aliphatic polyamide, semi-aromatic polyamide, aromatic polyamide, polyamide-11 ( Nylon-11), Polyamide-12 (Nylon-12), Polyamide-4,6, Polyamide-6 (Nylon-6), Polyamide-6,10, Polyamide- 6,12, polyamide-6,6 (nylon-6,6), polyamide-6,9, polyamide (PA) and mixtures of two or more thereof. The packaging material of claim 5, wherein the thermoplastic polymer is intermolecularly cross-linked with the torn single and/or multilayer graphene sheet, wherein on the tear edge of the sheet, the sheet has a reactive bond Position of the carbon atom. The packaging material of claim 5 or 6, wherein the graphene-reinforced polymer matrix includes at least one single and/or multilayer graphene nanoparticle bonded to one or more polymer molecules. The packaging material of any one of claims 5 to 7, wherein the graphene-reinforced polymer matrix comprises at least one thermoplastic polymer bonded or adhered to one or more mechanically exfoliated single or multilayer graphene nanoparticles molecular. The packaging material according to any one of claims 1 to 8, wherein the graphene-reinforced polymer matrix composite material is prepared by: (a) Dispersing graphite particles into a molten thermoplastic polymer phase, wherein at least 50% by weight of the graphite in the graphite particles is composed of multilayer graphite crystals with a thickness of 1.0 to 1000 microns along the c-axis direction; and (b) applying a series of shear strain events to the molten polymer phase so that the shear stress in the molten polymer phase is equal to or greater than the interlaminar shear strength (ISS) of the graphite particles, and In each event, the molten polymer phase continuously exfoliates the graphite until the graphite is at least partially exfoliated to form a single and multilayer graphene with a thickness of less than 10 nm along the c-axis direction in the molten polymer phase The distribution of nanoparticles. The packaging material according to any one of claims 1 to 8, which comprises one or more layers of graphene-reinforced polymer matrix composite materials. For example, the packaging material of claim 10 further includes one or more layers of materials including paper, plastic, metal, or a combination thereof. For example, the packaging material of claim 10 further includes one or more layers of foil or flexible ceramic material. A method for improving the barrier resistance of a polymer to permeate, which comprises forming a graphene-reinforced polymer matrix composite in the polymer by the following steps: (a) Disperse graphite particles into the molten thermoplastic polymer phase of the polymer, wherein at least 50% by weight of the graphite in the graphite particles is composed of multilayer graphite with a thickness of 1.0 to 1000 microns along the c-axis direction Crystalline composition; and (b) Apply a series of shear strain events to the molten polymer phase so that the shear stress in the molten polymer phase is equal to or greater than the interlaminar shear strength (ISS) of the graphite particles, and each event, the The molten polymer phase continuously mechanically exfoliates the graphite until the graphite is at least partially exfoliated to form a single and multilayer graphene nanoparticle with a thickness of less than 10 nm along the c-axis direction in the molten polymer phase Distribution. The method of claim 13, wherein the polymer is selected from the group consisting of acrylic resin, polymethyl methacrylate (PMMA), acrylonitrile, acrylonitrile butadiene styrene (ABS) copolymerization Compound, polyarylate, polyacrylonitrile (PAN), polyamide imide (PAI), aromatic polyimide, aromatic thermoplastic polyester, liquid crystal polymer, polyaryl ether-ketone, polycarbonate ( PC), polydimethylsiloxane (PDMS), polyaryl ether ketone (PAEK), polyether ether-ketone (PEEK), poly ethylene naphthyl dicarboxylate (PEN), polyether imide (PEI), Polyether Ketone (PEK), Polyethylene, Polyether Sulfate, Poly Sulfide (PSul), Polyethylene Sulfide (PES), Polyethylene Terephthalate (PET or PETE), Low Density Polyethylene (LDPE), high density polyethylene (HDPE), polyglycolic acid (PGA), polylactic acid (PLA), polylactic-glycolic acid copolymer (PLGA), polyoxymethylene plastic (POM/acetal), polystyrene Base ether, polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polypropylene (PP), polystyrene (PS), polyunion (PSU), polytetrafluoroethylene (PTFE/TEFLON®) , Polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), thermoplastic elastomer, polyimide, thermoplastic polyimide, ultra-high molecular weight polyethylene (UHMWPE), natural or synthetic rubber, polyamide (PA), nylon, aliphatic polyamide, semi-aromatic polyamide, aromatic polyamide, polyamide-11 (nylon-11), polyamide-12 (nylon-12), Polyamide-4, 6, polyamide-6 (nylon-6), polyamide-6,10, polyamide-6,12, polyamide-6,6 (nylon-6,6 ), polyamide-6,9, polyamide (PA) and a mixture of two or more thereof. The method of claim 13 or 14, wherein a series of shear strain events are applied until at least 50% by weight of the graphite is exfoliated to form a single and multiple layers of less than 10 nanometers in thickness along the c-axis in the molten polymer phase The distribution of graphene nanoparticles. The method of any one of claims 13 to 15, wherein a series of shear strain events are applied until at least 90% by weight of the graphite is exfoliated to form a polymer phase of less than 10 nm along the c-axis direction in the molten polymer phase The distribution of nanometer-thick single and multilayer graphene nanoparticles. The method according to any one of claims 13 to 16, wherein the permeate is gas or liquid. The method of claim 17, wherein the gas system is oxygen or carbon dioxide. Such as the method of claim 17, wherein the liquid system is water or fuel. A packaging material formed from the polymer of any one of claims 13 to 16. For example, the packaging material of claim 17 further includes paper, foil or flexible ceramic materials or a combination thereof. A product formed from the polymer of any one of claims 13 to 16, wherein the product is selected from the group consisting of: film, container, blister package, and blow molded article.

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