WO2018111568A2 - Élastomère composite polymère maléaté-oxyde de graphène et article contenant un élastomère composite - Google Patents

Élastomère composite polymère maléaté-oxyde de graphène et article contenant un élastomère composite Download PDF

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WO2018111568A2
WO2018111568A2 PCT/US2017/063914 US2017063914W WO2018111568A2 WO 2018111568 A2 WO2018111568 A2 WO 2018111568A2 US 2017063914 W US2017063914 W US 2017063914W WO 2018111568 A2 WO2018111568 A2 WO 2018111568A2
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maleated
composite elastomer
graphene oxide
polymer
sebs
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PCT/US2017/063914
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WO2018111568A3 (fr
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Christopher J ELLISON
Heonjoo HA
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Board Of Regents, The University Of Texas System
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/262—Polypropylene
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/28—Polymers of vinyl aromatic compounds
    • B01D71/281—Polystyrene
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/78—Graft polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D71/06—Organic material
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    • B01D71/80—Block polymers
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/21—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/218—Additive materials
    • B01D2323/2181—Inorganic additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

Definitions

  • the present disclosure relates to a method of forming a maleated polymer- graphene oxide composite elastomer and to articles, such as coatings, membranes, flexible devices, clothing, gas barriers, gas separation devices, and construction products containing the composite elastomer.
  • Materials containing polymers are used in a wide variety of applications, including anti-corrosion coatings, wearable devices, flexible displays, and devices for monitoring physiological signals.
  • Some polymers used in composites materials are commercially available, but recipes and methods of modifying them and forming materials and devices from them are often complex and the processing and application of such materials can be limited by the as-supplied material properties. Additionally, although polymers are inexpensive and lightweight, they often have other properties that are undesirable in some applications.
  • the present disclosure provides a maleated polymer-graphene oxide composite elastomer including a plurality of non-reduced graphene oxide (GO) fillers and a plurality of maleated polymers covalently bound to the plurality of graphene oxide fillers via maleic acid covalent bonds.
  • GO non-reduced graphene oxide
  • the present disclosure further provides a method of forming a maleated polymer-graphene oxide composite elastomer by reacting a plurality of maleic anhydride groups on a plurality of maleated polymers with a plurality of oxidative groups on a plurality of GO fillers to form a plurality of covalent bonds and to crosslink the plurality of maleated polymers via the plurality of GO fillers.
  • the present disclosure further includes any other maleated polymer-graphene oxide composite elastomers made by the above method.
  • the present disclosure further includes any of the above maleated polymer- graphene oxide composite elastomers located in a gas separation membrane, a gas separation system, a gas barrier membrane, a hydrophobic coating, an asphalt additive, a shingle additive, or a wearable device.
  • the above composite elastomers, methods of forming composite elastomers, and articles or devices in which composite elastomers are locate may be further characterized by any of the following additional features, which may be combined with one another unless clearly mutually exclusive:
  • the plurality of maleated polymers may include a plurality of styrene- ethylene-butylene-styrene grafted maleic anhydride triblock (SEBS-g-MA) copolymers, a plurality of maleated polyolefins, a plurality of maleic anhydride grafted polymers, or any combinations thereof;
  • SEBS-g-MA styrene- ethylene-butylene-styrene grafted maleic anhydride triblock
  • the plurality of maleated polyolefins include a plurality of maleated polyethylene (PE) or maleated polypropylene (PP), or any combinations thereof;
  • the plurality of maleic anhydride grafted polymers include a plurality of maleic anhydride grafted polystyrene (PS), polymethylmethacrylate (PMMA), polydimethyl siloxane (PDMS), polyamide (PA), polyethylene oxide (PEO), polypropylene oxide (PPO), or polyester (PET), or any combinations thereof;
  • the plurality of maleic anhydride grafted polymers incldue SEBS-g-MA; v) the plurality of non-reduced GO fillers has an average aspect ratio between 100 and 2000;
  • the plurality of non-reduced GO fillers has an average aspect ratio between 500 and 1600;
  • the plurality of non-reduced GO fillers has an average aspect ratio between 900 and 1200;
  • the composite elastomer has sufficient tensile strength to be stretched up to 100% of its length before failure
  • the composite elastomer has at least an about 70% increase in tensile strength as compared to a similar material comprising only the plurality of maleated polymers and not the plurality of non-reduced GO fillers; xii) the composite elastomer has at least about 2,000% increase in modulus as compared to a similar material comprising only the plurality of maleated polymers and not the plurality of non-reduced GO fillers.
  • the patent or application file contains at least one drawing executed in color.
  • FIG. 1A is a chemical structural diagram of GO with oxidative functional groups
  • FIG. IB is a chemical structural diagram of a SEBS-g-MA copolymer
  • FIG. 2 is a prior art graph of Young's modulus versus volume fraction for Voigt and Reuss models, as well as for dilute isotropic suspensions of platelets, fibers, and spherical particles embedded in a matrix;
  • FIG. 3 is a graph of modeling results using Voigt and Reuss upper and lower bounds, with the Y-axis (Young's modulus) plotted in log scale for clarity, the graph containing an insert of magnified data for dilute concentration;
  • FIG. 4A is a schematic diagram of a gas separation system including a maleated polymer-graphene oxide composite elastomer
  • FIG. 4B is a schematic diagram of another gas separation system including a maleated polymer-graphene oxide composite elastomer
  • FIG. 5 is a diagram of the hydrolysis reaction of neat SEBS-g-MA exposed to air or water;
  • FIG. 6A is a graph of Fourier transform infrared spectra of annealed SEBS-g-
  • FIG. 6B is a graph of selected region 3800-3600 cm "1 of Fourier transform infrared spectra of annealed SEBS-g-MA, after 3, 6, and 12 days at ambient temperature, the graph vertically shifted for clarity;
  • FIG. 6C is a graph of selected region 1900-1650 cm "1 of Fourier transform infrared spectra of annealed SEBS-g-MA, after 3, 6, and 12 days at ambient temperature
  • FIG. 6D is a graph of selected region 1200-800 cm "1 of Fourier transform infrared spectra of annealed SEBS-g-MA, after 3, 6, and 12 days at ambient temperature;
  • FIG. 7A is graph of Fourier transform infrared spectra of hydrolyzed SEBS (after 12 days of annealed SEBS-g-MA), annealed SEBS-g-MA, and SEBS-g- MA/GO composites after 12 days at ambient temperature for region 3800-600 cm "1 ;
  • FIG. 7B is a graph of selected region 3800-3600 cm "1 of Fourier transform infrared spectra of hydrolyzed SEBS (after 12 days of annealed SEBS-g-MA), annealed SEBS-g-MA, and SEBS-g-MA/GO composites after 12 days at ambient temperature;
  • FIG. 7C is a graph of selected region 1900-1650 cm "1 of Fourier transform infrared spectra of hydrolyzed SEBS (after 12 days of annealed SEBS-g-MA), annealed SEBS-g-MA, and SEBS-g-MA/GO composites after 12 days at ambient temperature;
  • FIG. 7D is a graph of selected region 1200-800 cm "1 of Fourier transform infrared spectra of hydrolyzed SEBS (after 12 days of annealed SEBS-g-MA), annealed SEBS-g-MA, and SEBS-g-MA/GO composites after 12 days at ambient temperature;
  • FIG. 8 is a photograph of a swelling experiment performed with neat SEBS-g- MA, and 1, 3, and 5 wt % GO composites in toluene;
  • FIG. 9 is a graph of the stress-strain curve of neat SEBS-g-MA, and 1, 3, and 5 wt % GO composites, with experiments performed at a strain rate of 500 mm/min;
  • FIG. 10A is a graph of thermal properties of neat SEBS-g-MA, and 1, 3, and 5 wt % GO composites characterized by differential scanning calorimetry at a cooling rate of 20 °C/min, each curve vertically shifted for clarity;
  • FIG. 10B is a graph of thermal properties of neat SEBS-g-MA, and 1, 3, and 5 wt % GO composites characterized by differential scanning calorimetry at a heating rate of 20 °C/min, each curve vertically shifted for clarity;
  • FIG. 11A is a diagram of a proposed chemical reaction Kl, which may take place between polymer SEBS-g-MA and GO;
  • FIG. 1 IB is a diagram of a proposed chemical reaction K2, which may take place between polymer SEBS-g-MA and GO
  • FIG. l lC is a diagram of a proposed chemical reaction K3, which may take place between polymer SEBS-g-MA and GO;
  • FIG. 1 ID is a diagram of a proposed chemical reaction K4, which may take place between polymer SEBS-g-MA and GO;
  • FIG. 12 is a graph of the stress-strain curve of neat SEBS-g-MA, and 1, 3, and
  • the present disclosure relates to a maleated polymer-graphene oxide composite elastomer and a method of forming a maleated polymer-graphene oxide composite elastomer by first ring-opening maleic anhydride rings of a SEBS-g-MA copolymer and then covalently bonding a GO filler to the SEBS-g-MA polymer via maleic acid covalent bonds.
  • the present disclosure also relates to articles containing a maleated polymer- graphene oxide composite elastomer, such as anti-corrosion coatings, membranes, gas separation membranes, gas separation coatings, gas barriers, gas separation devices, wearable devices, flexible devices, clothing, shoes and shoe soles, asphalt additives, shingle additives, road paving modifiers, and construction products.
  • a maleated polymer- graphene oxide composite elastomer such as anti-corrosion coatings, membranes, gas separation membranes, gas separation coatings, gas barriers, gas separation devices, wearable devices, flexible devices, clothing, shoes and shoe soles, asphalt additives, shingle additives, road paving modifiers, and construction products.
  • inorganic filler typically, as the content of inorganic filler increases, in the production of polymer/inorganic composite elastomer material, the material will decrease in elasticity. Because polymers are generally elastic, and inorganic fillers are generally brittle, a polymer/inorganic composite elastomer will typically display intermediate characteristics between those of the polymer and the inorganic filler individually. Accordingly, it is difficult and rare to create a composite elastomer that does not exhibit decreased elasticity when its mechanical strengths are increased significantly.
  • a maleated polymer-graphene oxide composite elastomer as disclosed herein may exhibit less or no decreased elasticity as its mechanical strengths are increased.
  • a maleated polymer-graphene oxide composite elastomer To form a maleated polymer-graphene oxide composite elastomer, the surface of a SEBS-g-MA copolymer may be protected because it may be hydrolyzed and ring-opened to form di-carboxylic acids on the copolymer by exposure to air or water.
  • One can prevent hydrolysis by keeping the SEBS-g-MA copolymer in dry conditions or annealing at an elevated temperature, such aas 120 °C overnight in vacuum.
  • the pristine, non-hydrolyzed SEBS-g-MA copolymer may then be reacted with a non-reduced GO filler at room temperature to form maleic acid covalent bonds between the copolymer and GO filler, resulting in a maleated polymer-graphene oxide composite elastomer.
  • the SEBS-g-MA copolymer may be dissolved in a solvent prior to reaction with non-reduced GO filler.
  • the non-reduced GO filler may be added to the SEBS-g-MA copolymer solution to allow reaction of maleic anhydride groups on the SEBS-g-MA copolymer with oxidative functional groups on the surface of the GO filler.
  • the entire method or one or more steps of it may take place at room temperature, for example at between 20°C and 30°C.
  • SEBS-g-MA copolymers react with the same GO filler, they are crosslinked via the GO filler.
  • many individual SEBS-g- MA copolymers will react with the same individual GO filler and any one individual SEBS-g-MA copolymer will also react with two separate individual GO fillers.
  • the cross-linked SEBS-g-MA copolymers and GO filler may form a macromolecular network in the maleated polymer-graphene oxide composite elastomer. At least 5%, at least 25%, or at least 50% of the SEBS-g-MA copolymers and GO filler, by weight, may be crosslinked.
  • the GO filler may be homogenously distributed in the maleated polymer-graphene oxide composite elastomer.
  • Suitable non-reduced GO filler may be produced by chemical functionalization and physical exfoliation of high purity, pre-oxidized graphite through stirring or sonication, such as using Hummer's method or a modification thereof.
  • the chemical structure of GO is shown in FIG. 1 A.
  • GO contains numerous oxidative functional groups, including hydroxyls, carboxylic acids, and epoxides, that are covalently bonded to the carbon-based benzene-like ring structure.
  • the resulting material is a sheet of carbon-based rings continuously arranged into a sheet as shown in FIG. 1A, with oxidative functional groups external to the sheet.
  • the hydroxyl and epoxide functional groups are typically present in a larger proportion than other functional groups, particularly when GO is produced using Hummer's method.
  • the oxidative functional groups typically include a variety of different functional groups, GO may also contain only one type of oxidative functional group, the epoxide functional group.
  • Reduced-GO is typically formed by treating GO with a chemical reducing agent, such as hydrazine, hydroiodic acid, and ascorbic acid, or by other methods which may include heat, sunlight, microwave, external energy or a combination of these. All of these methods reduce oxidative functional groups, which may include hydroxyl, epoxide, and carboxylic acid. However, even RGO retains some epoxide functional groups, they are just more limited in number than before reduction.
  • a chemical reducing agent such as hydrazine, hydroiodic acid, and ascorbic acid
  • the GO filler may have an average aspect ratio between 100 and 2000, between 500 and 1600, or between 900 and 1200.
  • the SEBS-g-MA copolymer is a styrene-ethylene-butylene-styrene ("SEBS") triblock copolymer grafted with maleic anhydride functional group.
  • SEBS styrene-ethylene-butylene-styrene
  • SEBS triblock copolymer grafted with maleic anhydride functional group.
  • the SEBS of SEBS-g-MA is described as being a triblock copolymer as opposed to a tetrablock copolymer because SEBS is synthesized by hydrogenating a triblock copolymer SBS (styrene-butadiene-styrene).
  • FIG. IB The chemical structure of a SEBS-g-MA copolymer is provided in FIG. IB. As shown, there is a 5-membered ring structure on the pendent group of the butylene segment.
  • the 5-membered ring structure is succinic anhydride, which is originated from maleic anhydride. Opening of this ring structure in hydrolyzed and ring-opened SEBS-g-MA copolymer may allow the formation of a maleic acid covalent bond with the GO filler.
  • SEBS-g-MA is used as an example throughout this application
  • other maleated polymers may be used in place of SEBS-g-MA or in combination with SEBS-g-MA or in combination with one another to covalently bond to GO.
  • These other polymers include maleated polyolefins, such as maleated polyethylene (PE) or maleated polypropylene (PP), and any other maleic anhydride grafted polymers such as maleic anhydride grafted polystyrene (PS), polymethylmethacrylate (PMMA), polydimethyl siloxane (PDMS), polyamide (PA), polyethylene oxide (PEO), polypropylene oxide (PPO), or polyester (PET).
  • PS maleated polyethylene
  • PP maleated polypropylene
  • PS maleated polystyrene
  • PMMA polymethylmethacrylate
  • PDMS polydimethyl siloxane
  • PA polyamide
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PET polyester
  • the maleated polymers may have a polymer molecular weight of between
  • a maleated polymer-graphene oxide composite elastomer as disclosed herein may have an elasticity that is almost unchanged, changed by less than 5%, or changed by less than 10% as compared to the polymer used to form it, such as the SEBS-g-MA copolymer. Elasticity may be represented by the elongation at break of the materials.
  • the composite elastomer may have a high elongation a break, allowing it to be stretched up to 100%>, up to 300%>, or even up to 500%> of its original length before failure.
  • a maleated polymer-graphene oxide composite elastomer as disclosed herein may have an increase in tensile strength of greater than 60%>, greater than 70%, or greater than 80%> as compared to the polymer used to form it, such as the SEBS-g-MA copolymer.
  • Tensile strength may be represented by the maximum strength or stress values before failure, as may be measured as described in ASTM D412, D638, and D1708. (ASTM International, PA, US).
  • a maleated polymer-graphene oxide composite elastomer as disclosed herein may have an increase in stress/strain Young's modulus of greater than 100%, greater than 1000%), or greater than 2,000%) as compared to the polymer used to form it, such as the SEBS-g-MA copolymer.
  • the stress/strain modulus may be measured as described in ASTM D412, D638, and D1708. (ASTM International, PA, US).
  • a maleated polymer-graphene oxide composite elastomer as disclosed herein may have sufficient mechanical integrity to be freestanding and to be formed in a variety of sizes as compared to the neat maleated polymer without GO.
  • the composite elastomer may also be bendable and flexible.
  • a maleated polymer-graphene oxide composite elastomer as disclosed herein may have high resistance to chemical reaction due to its cross-linked nature. For instance, when subjected to a solvent, a maleated polymer-graphene oxide composite elastomer as described herein may swell instead of dissolving away, as shown in FIG. 8. Due to the presence of the GO filler, the maleated polymer-graphene oxide composite elastomer may appear brownish at low concentrations of GO, and may appear black with high concentrations of GO. This provides high resistance to degradation by UV light, visible light, or both. Because most of the polymers are susceptible to oxidation caused by UV light, the material may appear more yellow as it is exposed to UV light. One or both of the resistance to chemical reaction or resistance to degradation by UV light, visible light, or both may contribute to high weatherability of the maleated polymer-graphene oxide composite elastomer.
  • a maleated polymer-graphene oxide composite elastomer as disclosed herein may have at least two of the elasticity properties, tensile strength, Young's modulus, abrasion resistance, bendability and flexibility, resistance to chemical reaction, resistance to degradation by UV light, visible light, or both, and weatherability described above and elsewhere herein.
  • a maleated polymer-graphene oxide composite may contain between 0-30 wt% GO. It may have a cross-linking density of between 10-95%, depending in the GO amount, with cross-linking density varying directly with GO amount.
  • the properties of the maleated polymer-graphene oxide composite elastomer may vary based on the chemical structure or type(s) of the polymer molecular weight of the polymer, the type of GO filler, the concentration of GO filler in the maleated polymer-graphene oxide composite elastomer, and the amount of crosslinking in terms of the % by weight of crosslinked material or as determined by another measure of crosslinking.
  • Theoretical models were generated to examine how the GO filler is dispersed and aligned in a matric formed by the SEBS-g-MA copolymer when the maleated polymer-graphene oxide composite elastomers are formed.
  • FIG. 2 is a graph of Young's modulus versus volume fraction for Voigt and Reuss models, as well as for dilute isotropic suspensions of platelet, fiber, and spherical particle fillers embedded in a polymer matrix.
  • FIG. 3 is a graph of modeling results using Voigt and Reuss upper and lower bounds, with the Y-axis (Young's Modulus) plotted in log scale for clarity, the graph containing an insert of magnified data for dilute concentration.
  • the maleated polymer-graphene oxide composite elastomer described herein lies in between the two models and is generally consistent with both.
  • the results of FIG. 3 indirectly indicate that the individual GO fillers incorporated in the SEBS-g-MA copolymer matrix are randomly dispersed without any specific alignment. This is supported by the fact that anisotropic composite elastomers typically offer superior strength and stiffness in comparison with isotropic composites elastomers.
  • anisotropic maleated polymer-graphene oxide composite elastomer described herein are exemplary materials for many applications, such as coatings that may be subjected to stress in multiple directions.
  • Articles containing a maleated polymer-graphene oxide composite elastomer may include anti-corrosion coatings, membranes, gas separation membranes, gas separation coatings, gas barriers, gas separation devices, wearable devices, flexible devices, clothing, shoes and shoe soles, asphalt additives, shingle additives, road paving modifiers, and construction products.
  • Gas permeability of a membrane is determined by two components.
  • One component is the solubility of molecules of the gas in the membrane, which allows the molecules to dissolve into the membrane, then exit the other side. Solubility links the concentration of the molecule of gas in the gas phase to the concentration of the molecules of gas in the membrane.
  • the other component is the diffusivity of a molecule of the gas through the membrane. Diffusivity is a kinetic property that reflects the effects of the surrounding membrane environment, such as small channels, on the motion of molecules of gas through the membrane. Solubility and diffusivity tend to be influenced by different properties of the membrane or gas as a result.
  • Gas permeability is a product of both solubility and diffusivity, such that a significant decrease in either factor lowers gas permeability overall.
  • gas permeability depends much more on the relative solubility of a specific gas molecule, than on the diffusivity of the gas. Therefore, the polymer is more permeable to large, soluble and condensable molecules than to small penetrants.
  • diffusivity is more strongly affected than the solubility.
  • GO fillers introduce tortuous pathways and modify the microstructure of the composite elastomer rather than its interactions with the gas, and as a result, its size-selective capability increases.
  • a maleated polymer-graphene oxide composite elastomer membrane may be used as a gas barrier.
  • the single gas permeability of a maleated polymer-graphene oxide composite elastomer membrane may vary based on factors such as the concentration of or the alignment of the GO filler. It may also be affected by the thickness of the membrane.
  • a gas barrier membrane may have a thickness of between 10 nm and 500 ⁇ .
  • Gas barrier membranes may be formed as free-standing membranes of one or more layers of maleated polymer-graphene oxide composite elastomer, or they may include supporting materials, such as metal foil or other tough or malleable material.
  • the maleated polymer-graphene oxide composite elastomer may be used in place of the gas barrier component for any given gas in any given gas barrier membrane or other gas barrier device.
  • a maleated polymer-graphene oxide composite elastomer as described herein may be used as any type of gas barrier in any application, it may have particular uses as well.
  • it may be used in building materials, for example as a water barrier or radon gas barrier.
  • It may be used as protective barriers, for instance in manufacturing and industrial processes where they contain poisonous or corrosive gasses, flammable gasses, or gasses, such as hydrocarbon gasses, that may have deleterious effects to human health or the environment after long-term exposure. It may also be used to contain harmful gasses present in the environment or released during environmental remediation.
  • it may be used to contain nuisance gasses, such as sulfide gasses produced by sewage processing and treatment.
  • the gas separation capacity of the maleated polymer-graphene oxide composite elastomer may be particularly influenced by the amount and type of GO filler. Increased concentration of GO filler increases the tortuosity of the path through which a gas may diffuse, slowing passage of gasses with larger kinetic diameters much more than passage of gasses with smaller kinetic diameters. Aspect ratio of the GO filler may also decrease diffusivity of gasses, affecting those with larger kinetic diameters more than those with smaller kinetic diameters.
  • Maleated polymer-graphene oxide composite elastomer membranes described herein may separate at least two gasses between 2.6 Angstroms and 5.0 Angstroms in size.
  • Gas separation membranes may also be formed as freestanding membranes of one or more layers of maleated polymer-graphene oxide composite elastomer. They may also include support materials, as long as the support materials do not impede gas separation.
  • gas separation membrane 20a in FIG. 4A includes maleated polymer-graphene oxide composite elastomer 30a surrounded by a frame 40, which may facilitate air-tight seal and also to make the gas separation membrane 20a easier to install, inspect, and replace.
  • Gas separation membrane 20b in FIG. 4B includes maleated polymer-graphene oxide composite elastomer 30b formed upon a gas- permeable support 140.
  • a gas separation system 10 may include a gas source 60, such as waste gas or exhaust, that includes at least one separable gas 70a and at least one non-separable gas 70b.
  • Gas from gas source 60 flows through compressor 80, which may be optional in some gas separation systems.
  • Compressed gas from compressor 80 enters intake chamber 100 or gas separation chamber 90 where molecules of separable gas 70a are separated from molecules of non-separable gas 70b.
  • Molecules of non-separable gas 70b may be returned via return pathway 190 to a flow pathway from gas source 60 either before compressor 80, as shown, or after compressor 80 (not shown).
  • molecules of non-separable gas 70a removed from intake chamber 100 may simply be released into the air.
  • Molecules of separable gas 70a pass through gas separation membrane 20 and enter separated gas output chamber 110. Molecules of separable gas 70a then exit gas separation chamber 90 and enter output container 120.
  • gas separation membrane 20a divides intake chamber 100a from separated gas output chamber 110a.
  • Frame 40 of gas separation membrane 20a may form an air-tight seal with other elements of gas separation chamber 90a between intake chamber 100a and separated gas output chamber 110a so that gas in intake chamber 100a may only enter separated gas output chamber 110a by passing through gas separation membrane 20a.
  • Separable gas 70a in separated gas output chamber 110a may be moved to output container 120 via a vacuum or partial vacuum, via air flow, or due to concentration differences.
  • Non-separable gas 70b and any remaining separable gas 70a in intake chamber 100a may be removed via an air flow, such as an air flow between intake vent 150 and outtake vent 160.
  • Gas in intake chamber 100a may also be removed by other mechanisms, such as a vacuum or partial vacuum or due to concentration differences.
  • GO alignment in a maleated polymer-graphene oxide composite elastomer for use as a gas barrier or in gas separation may be perpendicular to the gas transport direction.
  • gas separation membrane 20b is formed on gas-permeable support 140 and located inside separated gas output chamber 1 10b.
  • Intake chamber 100b is located inside gas separation membrane 20b.
  • Intake chamber 100b may also extend beyond gas separation membrane 20b and separated gas output chamber 1 10b, as shown, or it may be located entirely within separated gas output chamber 1 10b, or entirely within gas separation membrane 20b (not shown).
  • Gas separation membrane 20b may also form an air-tight seal between intake chamber 100b and separated gas output chamber 1 10b so that gas in intake chamber 100b may only enter separated gas output chamber 1 10b by passing through gas separation membrane 20b.
  • Separable gas 70a in separated gas output chamber 1 10b may be removed and moved to output container 120 via an air flow, such as an air flow between intake vent 170 and outtake vent 180. It may also be removed by other mechanisms, such as a vacuum or partial vacuum or due to concentration differences.
  • 100b may be removed via air flow through the chamber, or by a vacuum or partial vacuum or due to concentration differences. It travels via
  • a mixture of separable gas 70a and non-separable gas 70b may be separated using gas separation system 10 in a continuous fashion or in an iterative fashion.
  • gas separation system including a maleated polymer-graphene oxide composite elastomer as described herein, such as gas separation system 10 at least 25%, at least 50%, at least 75%, at least 90%, at least 95%, at least 99%, or at least 99.9% of separable gas may be removed from a mixture of separable gas and non- separable gas.
  • the separable gas thus obtained may contain no more than 10% non- separable gas, no more than 5% non-separable gas, no more than 1% non-separable gas, no more than 0.5% non-separable gas, or no more than 0.1% non-separable gas.
  • a maleated polymer-graphene oxide composite elastomer may be used in place of the gas separation component for any given gas in any given gas separation membrane or other gas separation system or device, such as hollow fiber gas separator and modules using hollow fiber gas separators.
  • a maleated polymer-graphene oxide composite elastomer as described herein may be formed in a variety of shapes and sizes, such as membrane or coatings on other articles, for example, gas separation membranes and gas barrier coatings and anti-corrosion coatings.
  • a maleated polymer-graphene oxide composite elastomer as described herein may also be used as a hydrophobic coating.
  • a maleated polymer-graphene oxide composite elastomer of this disclosure may also be used as a desalination membrane, or in wearable devices, flexible displays, and devices for monitoring physiological signals.
  • a maleated polymer-graphene oxide composite elastomer as described herein may be incorporated in asphalt, road paving modifiers, and shingles as an additive.
  • Asphalt is a sticky, black and highly viscous liquid or semi-solid form of petroleum, which is often used as the glue or binder mixed with aggregate particles to create asphalt concrete.
  • Asphalt concrete is often used for road paving and is often modified with various polymers used as road paving modifiers, depending on the parameters necessary.
  • Asphalt is also often used for bituminous waterproofing products, for instance, in the production of roofing felt and for sealing flat roofs.
  • Many non-flat roofs are covered with waterproof shingles, which are typically flat, rectangular shapes arranged on a roof with each successive section overlapping the joints below.
  • Shingles may be made of composite materials, for example, asphalt shingles.
  • the protective nature of asphalt shingles primarily comes from its long-chain petroleum hydrocarbons; however, the use or incorporation of maleated polymer-graphene oxide composite elastomer may provide additional mechanical strengths to the shingles.
  • a maleated polymer-graphene oxide composite elastomer of the present disclosure may be incorporated in wearable devices, such as watch and fitness or activity tracking bands, medical device straps (e.g., heart rate monitors), shoe soles and bodies, and headsets, headphones, or wearable cameras. Because such wearable devices rely on certain components to withstand weather conditions and rigors of everyday wear, the mechanical strengths at least of those components may benefit from a maleated polymer-graphene oxide composite elastomer as described herein.
  • maleated polymer-graphene oxide composite elastomers as described herein may be soft in texture and biodegradable, which are important criteria for wearable devices, due to the intimae contact with human skin.
  • acrylates are generally brittle and absorb a considerable amount of water due to their polar chemical structure.
  • a maleated polymer-graphene oxide composite elastomer as described herein is elastic, facilitating wear-ability, and hydrophobic, repelling water.
  • Example 1 Maleated polymer-graphene oxide composite elastomer formation and basic characterization
  • the SEBS-g-MA copolymer (Kraton ® FX1901) was used after annealing at 120 °C in vacuum oven.
  • the styrene to rubbery ratio of the SEBS-g-MA copolymer was about 3 to 7 (w/w) and maleic anhydride was functionalized at approximately 2 wt%, based on the vendor's SEBS-g-MA copolymer data sheet.
  • Non-reduced GO filler was prepared using a modified Hummer's method. Tetrahydrofuran (THF) and toluene were purchased from Fisher Chemical and used without any further purification.
  • SEBS-g-MA copolymer After heating the SEBS-g-MA copolymer, certain amounts of SEBS-g-MA copolymer were dissolved in TUF at room temperature with the prepared GO filler while stirring. For example, in order to prepare SEBS-g-MA/1 wt % GO composite elastomer, 495 mg of SEBS-g-MA copolymer was dissolved in 6 mL of TUF, and then 5 mg of GO filler was incorporated into the solution. Once the SEBS-g-MA copolymer and GO filler were dispersed in TUF, the solution was poured into a polytetrafluoroethylene (PTFE) dish and solution casted at room temperature for 1 day. Because the crosslinking reaction takes place slowly even at room temperature, the material was characterized for 2 weeks using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR).
  • ATR-FTIR attenuated total reflection Fourier transform infrared spectroscopy
  • FIGS. 6A-D represent the FTIR spectra of as-prepared neat SEBS-g-MA copolymer, after 3, 6, and 12 days.
  • most of the peaks related to the SEBS backbone, such as CH 2 , CH 3 stretching (2600 cm ' ⁇ OOO cm “1 ) and aromatic ring stretching (around 1400 cm “1 ) are unchanged.
  • FIGS. 6A-D indicate that maleic anhydride functional groups on the SEBS main chain are highly reactive, and hydrolyze slowly at room temperature by forming two carboxylic acid groups.
  • FIGS. 7A-D represent the FTIR data for SEBS-g-MA/GO composite elastomers with different concentrations of GO fillers after 12 days at ambient conditions. Similar to FIG. 6A, all of the major peaks referring to the main chain SEBS essentially did not change with increasing GO filler concentration (FIG. 7 A).
  • Example 2 Mechanical properties of SEBS-g-MA/GO composite elastomers
  • tensile strength, elongation at break, and Young's modulus results are shown in FIG. 9 and Table 1, below.
  • FIG. 9 is a graph of the stress-strain curve of neat SEBS-g-MA copolymer, and 1, 3, and 5 wt % GO filler maleated polymer-graphene oxide composite elastomers, with experiments performed at a strain rate of 500 mm/min.
  • microtensile specimens were prepared by solution casting a thin film (thickness 0.15 ⁇ 0.02 mm) of each sample on a mold (i.e., to produce a dog bone sample with a gauge length of 22 mm, width of 4.8 mm and thickness of about 0.15 mm) and punching out a specimen in a shape satisfying ASTM D1708-13 standards.
  • An Instron (model 5966) equipped with a 1 kN load cell was used with a strain rate of 100 mm/min (i.e., at this gauge length this is a nominal strain rate equivalent to 500 mm/min for ASTM D638 standard samples, which is the recommended speed for highly elastic rubber samples) and samples were tested in triplicate.
  • Table 1 Mechanical properties of neat SEBS-g-MA and GO composite elastomers. 3 ⁇ 4 « SHBS ⁇ A I&S & U ? « 1 3 ⁇ 4S i3 ⁇ 4
  • the SEBS-g-MA/GO composite elastomers showed a significant increase in tensile strength and modulus [which one?], with almost no decrease in elongation at break.
  • tensile strength increased -65%
  • tensile modulus increased -2,660 %.
  • composites will display a significant loss in elasticity as inorganic fillers are incorporated into a flexible polymer, such as a SEBS- g-MA copolymer.
  • the results of FIG. 9 and Table 1 may be due to: (1) the formation of crosslinks via covalent bonds, increasing the mechanical integrity of the composite elastomer; and (2) crosslinking of the GO filler to the pendent group of the SEBS-g- MA copolymer instead of the main chain.
  • the strong elasticity of the composite elastomer is likely due to the main chain of SEBS because SEBS is a thermoplastic elastomer. If the GO filler covalently bound the copolymer's main chain, elasticity would be lost due to the rigidity of the GO filler itself.
  • the GO fillers are covalently bound to the grafted maleic anhydride group and maleic anhydride was present at a concentration low enough that macromolecular mobility was not affected.
  • the thermal properties of neat SEBS-g-MA copolymer and 1, 3, and 5 wt % GO composite elastomers were almost identical.
  • the glass transition temperature (T g ) and melting temperature of EB block (T m ,a) of all of the materials were essentially identical.
  • the melting temperature of small impurities EB block copolymer not chemically bonded to styrene block, ⁇ ⁇ ; ⁇ ) showed a slight increase due to the GO filler acting as a nucleating agent, but the peak was insignificant in relation to other thermal transitions.
  • Example 4 Chemical reactions of the SEBS-g-MA/GO composite elastomers Proposed chemical reactions that may take place between a SEBS-g-MA copolymer and a GO filler are schematically illustrated in FIGS. 11 A-D, based at least on the results shown in FIGS. 6-9. It is more likely that most reactions will follow reaction Kl of FIG. 11A or reaction K4 of FIG. 11D, rather than reaction K2 of FIG 11B or K3 of FIG. 11C because carboxylic acids are more reactive than anhydrides, and epoxies are more reactive than hydroxyls.
  • one carboxylic acid may act as an acid catalyst, which would favor the other carboxylic acid group reacting with epoxies or hydroxyls on the surface of the GO filler, as shown in reaction Kl of FIG. 11A and reaction K2 of FIG. 11B.
  • Reaction K3 of FIG. 11C is possible if a carboxylic acid group is in close proximity, such as if present on the surface of the GO filler. However, reaction K3 is much less likely to occur as compared to reactions Kl and K2 when the reactivity and the scarceness of carboxylic acid groups on the GO filler are considered. Reaction K4 could be also possible with the presence of water molecule in air.
  • reaction K4 will crosslink in one single reaction where both maleic anhydride and epoxy groups are ring-opened. Further, maleic anhydrides may react quickly with epoxy groups even at room temperature. As such, reaction K4 is often used for epoxy adhesives.
  • reaction K3 of FIG. l lC played an important role in increasing the mechanical integrity of the SEBS-g- MA/GO composite elastomer, while maintaining the elasticity of the composite elastomer.
  • all samples were heated at 160 °C for 24 hours in a vacuum oven after solution casting. Because the maleated polymer-graphene oxide composite elastomer was heated at an elevated temperature, no water molecule was present and hydrolysis of maleic anhydride group was successfully prevented. Thus, the maleated polymer-graphene oxide composite elastomer favorably underwent only reaction K3.
  • FIG. 12 is a graph of the stress-strain curve of neat SEBS-g-MA copolymer, and 1, 3, and 5 wt % GO composite elastomers after annealing, with experiments performed at a strain rate of 500 mm/min.
  • the mechanical properties of the maleated polymer-graphene oxide composite elastomer after annealing showed a trend typical of a composite elastomer. In this trend, as the concentration of GO filler increases, tensile strength and Young's modulus increase gradually, but elasticity significantly decreases.
  • results of FIG. 12 provide clear contrast to those of FIG. 9 and Table 1 above, where elasticity was maintained while other mechanical properties increased substantially. Accordingly, the results of FIG. 12 indirectly indicate that the majority of the chemical reactions occur either by reactions Kl, K2, or K4, illustrated in FIG 11 A, 11B, and 11D, respectively.

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Abstract

La présente invention concerne un élastomère composite polymère maléaté-oxyde de graphène comprenant une pluralité de charges à base d'oxyde de graphène non réduit et une pluralité de polymères maléatés liés de manière covalente à la pluralité de charges à base d'oxyde de graphène par l'intermédiaire de liaisons covalentes de l'acide maléique. La présente invention concerne en outre un procédé de formation d'un élastomère composite polymère maléaté-oxyde de graphène par réaction d'une pluralité de groupes anhydride maléique se trouvant sur une pluralité de polymères maléatés avec une pluralité de groupes oxydants se trouvant sur une pluralité de charges à base d'oxyde de graphène pour former une pluralité de liaisons covalentes et pour réticuler la pluralité de polymères maléatés par l'intermédiaire de la pluralité de charges à base d'oxyde de graphène. La présente invention concerne en outre un quelconque autre élastomère composite polymère maléaté-oxyde de graphène obtenu par le procédé ci-dessus.
PCT/US2017/063914 2016-12-14 2017-11-30 Élastomère composite polymère maléaté-oxyde de graphène et article contenant un élastomère composite WO2018111568A2 (fr)

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CN112724583A (zh) * 2020-12-29 2021-04-30 宁波庸禾新材料科技有限公司 一种石墨烯功能化热塑性弹性体复合材料及其制备方法
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US11958584B2 (en) 2018-11-26 2024-04-16 Sceye Sa Graphene-oxide grafted PBO (Zylon®) fibers; method for production and applications to airship hulls and lighter than air vehicles
CN110157370A (zh) * 2019-05-14 2019-08-23 永隆高新科技(青岛)有限公司 一种封边用反应型聚氨酯热熔胶
WO2021007648A1 (fr) * 2019-07-17 2021-01-21 Solmax International Inc. Membrane polymère contenant du graphène
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CN110564092B (zh) * 2019-08-13 2021-06-22 滁州职业技术学院 一种pmma/石墨烯纳米薄膜材料的制备方法及其应用
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