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    • 专利摘要:
    polymer nanocomposite formation method. the present invention relates to a method for forming a polymer composite, which comprises mixing a thermoset polymer precursor, and from 0.01 to 30% by weight of a derivatized nanoparticle based on the total weight of the polymer composite, wherein the derivatized nanoparticle includes functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactone, functionalized polymeric or oligomeric groups, or a combination comprising at least least one of the above functional groups.
    公开号:BR112013005666B1
    申请号:R112013005666-5
    申请日:2011-09-09
    公开日:2020-09-01
    发明作者:Gaurav Agrawal；Soma Chakraborty；Ping Duan；Michael H. Johnson
    申请人:Baker Hughes Incorporated；
    IPC主号:
    专利说明:

    [0001] The present patent application claims the benefit of US Application 12 / 878,507, filed on September 9, 2010, which is hereby incorporated by reference in its entirety. BACKGROUND
    [0002] A downhole environment such as, for example, an oil or gas well in an oil field or an underwater environment, a geothermal drilling hole, a carbon dioxide sequestration hole, and other such environments downhole, it can expose the equipment used in these environments to harsh conditions of temperature, pressure or corrosion. For example, equipment such as compactors, preventive eruption controllers, drill motors, drill bits, etc., may be exposed to downhole conditions that can affect the integrity or performance of the element and tools, and in particular the performance of the components of these tools made of plastic.
    [0003] Plastic components or coatings that have thermal, mechanical and barrier properties are used in downhole environments that have a variety of such different and challenging conditions. These components can, however, be damaged by the high temperature, corrosive or lipophilic conditions found in rock bottom conditions. Where the article is an element that has a rubber or plastic part or liner, downhole conditions can cause, for example, swelling by the absorption of hydrocarbon oil, water or brine, or other materials found in such environments. This swelling can weaken the structural integrity of the element or cause the element to have poor dimensional stability, which results in difficulty in placing, activating or removing the element.
    [0004] The components and / or plastic bottom coatings can be formed from polymeric nanocomposites of polymers and additives with nanodimensions, where the combination has desirable mechanical and / or barrier properties. Uniform (homogeneous) mixing is necessary during the formation of such polymer nanocomposites to avoid problematic behavior, such as gel formation, and therefore mixing can be a technical challenge. SUMMARY
    [0005] The above and other deficiencies of the prior art are overcome, in one embodiment, by a method for the formation of a polymer composite, which comprises the mixing of a thermoset polymer precursor and from 0.01 to 30% by weight of a derivatized nanoparticle based on the total weight of the polymer composite, wherein the derivatized nanoparticle includes functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactone, polymerized or functionalized oligomeric groups, or a combination comprising at least one of the above functional groups.
    [0006] In another embodiment, a method for producing a polymer composite comprises derivatizing a nanoparticle to include functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl , alkaryl, lactone, functionalized polymeric or oligomeric groups, or a combination comprising at least one of the above functional groups, and mixing the derivatized nanoparticle with a thermosetting polymer precursor.
    [0007] In another embodiment, a method for forming a polyurethane nanocomposite comprises derivatizing a nanoparticle to include functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactone, functionalized polymeric or oligomeric groups, or a combination comprising at least one of the above functional groups, and mixing 0.05 to 20% by weight of derivatized nanoparticle, a precursor to a polyurethane, polyester bound with urethane, or urea-bound polyester comprising a composite that has at least two isocyanate groups, and a polyol, a diamine, or the combination thereof, wherein the amount of derivatized nanoparticle is based on the total weight of the polyurethane nanocomposite. BRIEF DESCRIPTION OF THE DRAWINGS
    [0008] Referring now to the drawings in which the identical elements are numbered identically in the various figures: FIG. 1 shows a reaction scheme for nanographene derivatization; FIG. 2 is a photograph showing (A) a non-derivatized nanographene suspended in N, N'-dimethyl formamide (DMF), and (B) a DMF derivatized nanographene; FIG. 3 shows graphs of elongation (A) and the tensile strength limit (B) versus examples of polymeric control without nanoparticles; FIG. 4 shows graphs of the tensile strength limit (A), the elongation (B) and the average modulus (C) versus the mixing time for comparative polymer composites containing nano clay; FIG. 5 shows graphs of the tensile strength limit (A), the elongation (B) and the average modulus (C) versus the application of vacuum for comparative polymer composites containing nano-clay; FIG. 6 shows graphs of the tensile strength limit (A), the elongation (B) and the average modulus (C) versus the mixing time for comparative nanographite polymer composites; FIG. 7 shows graphs of the tensile strength limit (A), the elongation (B) and the average modulus (C) versus the vacuum application for comparative polymer composites containing nanographite; FIG. 8 shows graphs of the tensile strength limit (A), the elongation (B) and the average modulus (C) versus the no-particle load for comparative polymer composites containing nano-clay; FIG. 9 shows graphs of the tensile strength limit (A), the elongation (B) and the average modulus (C) versus the no-particle load for comparative polymer composites containing nanographite; FIG. 10 shows graphs of the tensile strength limit (A), the elongation (B) and the average module (C) for the polymeric control, comparative composite containing 1% by weight of nanographite, and polymer composite containing nanographene derivatized with 0.9% by weight phenethyl alcohol; FIG. 11 is a comparative graph of the tensile strength limit for comparative control polymers (without nanoparticles), nano-clay, and polymer composites containing nanographite, and a polymer composite containing an exemplifying derivatized nanographene; FIG. 12 is a comparative plot of elongation for comparative control polymers (without nanoparticles), nano-clay, and polymer composites containing nanographite, and a polymer composite containing exemplified derivatized nanographene; FIG. 13 is a comparative graph of the average module for comparative control polymers (without nanoparticles), nano-clay, and polymer composites containing nanographite, and a polymer composite containing exemplified derivatized nanographene; FIG. 14 is a diffusion graph comparing the percentage of elongation versus the tensile strength limit for comparative examples of non-derivatized nanoparticles (including nanographite) in polymer composites, and for a polymer composite containing exemplary derivatized nanographene; and FIG. 15 is a graph of stress versus strain for a comparative example of control of a polyurethane nanocomposite and an exemplifying polyurethane nanocomposite with derivatized nanographene. DETAILED DESCRIPTION
    [0009] Here is presented a method for the formation of a polymer non-composite of a polymer and a derivative nanoparticle. It has been surprisingly found that the inclusion of a na-noparticle, derivatized to include a functional group such as a hydroxy, carboxy, epoxy, or other functional group, acts as a dispersion aid during the formation of nanocomposites. In other embodiments, it has been found that rotary mixing provides a highly uniform mixture of nanoparticles derivatized in reactive formulations that include polyisocyanate-based compositions such as polyurethanes and / or polyureas. The inclusion of derivatized nanoparticles in polymer nanocomposites can provide increased mechanical properties such as the percentage of elongation, the tensile strength limit, and other properties, in relation to the polymer not modified with a derivatized nanoparticle, or a polymer or polymer nanocomposite. then identical prepared with nanoparticles that have not been derivatized. In addition, it was also surprisingly found that the variability in mechanical properties, including those mentioned above, is significantly reduced when a derivatized nanoparticle is included in the composite, when compared to the inclusion of a non-derivatized nanoparticle. In this way, the mechanical properties of composites of any material from a variety of polymeric materials, such as, for example, polyurethanes and polyurethane foams, can be enhanced to obtain more mechanically and dimensionally robust articles that can withstand challenging downhole conditions. high temperature, pressure and corrosion.
    [00010] The method for forming the polymer composite includes mixing a thermoset polymer precursor and a derivatized nanoparticle. Nanoparticles are derivatized to include chemical functional groups to increase dispersibility, reactivity, surface properties, compatibility, and other desirable properties. Combinations comprising derivatized and non-derivatized nanoparticles will also be used.
    [00011] Nanoparticles, from which de-rivatized nanoparticles are formed, are generally particles that have an average particle size in at least one dimension, less than one micrometer (pm). As used herein, "average particle size" refers to the numerical average particle size based on the largest linear particle size (sometimes referred to as "diameter"). The particle size, including the average, maximum and minimum particle sizes, can be determined by an appropriate particle sizing method such as, for example, static or dynamic light scattering (SLS or DLS) using a light source laser. Nanoparticles can include particles that have an average particle size of 250 nm or less, or particles that have an average particle size of more than 250 nm at less than 1 pm (sometimes indicated in the prior art as particles "with submicron sizes"). In one embodiment, a nanoparticle can have an average particle size of about 0.01 to about 500 nanometers (nm), specifically from 0.05 to 250 nm, more specifically from about 0.1 to about 150 nm , more specifically from about 0.5 to about 125 nm, and even more specifically from about 1 to about 75 nm. Nanoparticles can be monodispersed, where all particles are the same size with little variation, or polydispersed, where particles have a size range and are averaged. Polydispersed nanoparticles are generally used. Nanoparticles of different particle average sizes can be used, so the particle size distribution of the nanoparticles can be unimodal (showing a single distribution), bimodal showing two distributions, or multimodal, showing more than one size distribution of particle.
    [00012] The minimum particle size for the smallest 5 percent of nanoparticles can be less than 0.05 nm, specifically less than or equal to 0.02 nm, and more specifically less than or equal to 0.01 nm. Similarly, the maximum particle size for 95% of nanoparticles is greater than or equal to 900 nm, specifically greater than or equal to 750 nm, and more specifically greater than or equal to 500 nm.
    [00013] Nanoparticles have a large surface area of more than 300 m2 / g, and in a specific modality from 300 m2 / g to 1,800 m2 / g, specifically from 500 m2 / g to 1,500 m2 / g.
    [00014] The nanoparticle presented here comprises a fullerene, a nanotube and a single or multiple wall, nanographite, nanographene, graphene fiber, nanodiamonds, polysilksquioxanes, silica nanoparticles, nano-clay, metal particles, or combinations that comprise at least one of the above.
    [00015] Fullerenes, as indicated herein, can include any form of hollow allotropic forms of the known carbon cage type that have a polyhedral structure. Fullerenes can include, for example, from about 20 to about 100 carbon atoms. For example, C60 is a fullerene that has 60 carbon atoms and great symmetry (Dsh), and is a relatively common commercially available fullerene. Exemplary fullerenes can include C30, C32, C34, C38, C40, C42, C44, C46, C48, C50, C52, C60, C70, C76, and others.
    [00016] Nanotubes can include carbon nanotubes, inorganic nanotubes, metallized nanotubes, or a combination comprising at least one of the above elements. Carbon nanotubes are tubular fullerene structures that have open or closed ends and that can be inorganic or made entirely or partially of carbon, and can also include components such as metals or metalloids. Nanotubes, including carbon nanotubes, can be single-walled nanotubes (SWNTs) or multi-walled nanotubes (MWNTs).
    [00017] Nanographite is a graphite sheet agglomerate of sheets, in which the layers of a stacked structure of one or more graphite layers, which have a two-dimensional plate-like structure of fused hexagonal rings with a K- system electrons, are stacked and loosely linked to each other through a π-π stacking interaction. The nanographite has micro- and nanoscale dimensions such as, for example, an average particle size of less than 1 pm, specifically from 1 to 15 pm, and an average (the smallest) dimension in nanoscale dimensions, and a average thickness less than 1 pm, specifically less than or equal to 700 nm, and even more specifically less than or equal to 500 nm.
    [00018] In one embodiment, the nanoparticle is a graphene that includes nanographene and graphene fibers (that is, graphene particles that have a larger average dimension of more than 1 mm and an aspect ratio of more than 10, where graphene particles form an interconnected chain). Graphene and nanographene, as indicated here, are effectively two-dimensional particles of nominal thickness, containing one or more layers of hexagonal rings fused with an extended delocalized K-electron system, stacked and loosely connected to each other through an interaction of stacking π-π. Graphene in general, and including nanographene, can be a single sheet or a stack of several sheets that have micro and nanoscale dimensions, as in some embodiments an average particle size from 1 to 20 pm, specifically from 1 to 15 pm, and a dimension (the smallest) of average thickness in nanoscale dimensions less than or equal to 50 nm, specifically less than or equal to 25 nm, and more specifically less than or equal to 10 nm. An exemplifying nanograph can have an average particle size of 1 to 5 pm, and specifically 2 to 4 pm. In addition, smaller nanoparticles or particles with submicron size as defined above can be combined with nanoparticles that have an average particle size greater than or equal to 1 pm. In a specific embodiment, the derivatized nanoparticle is a derivatized nanograph.
    [00019] Graphene, including nanographene, can be prepared by exfoliating the nanographite or by a synthetic procedure by "unziping" a nanotube to form a nanographene strip, followed by derivatisation of the nanographene to prepare, for example, nanographene oxide .
    [00020] Exfoliation to form graphene or nanographene can be performed by exfoliating a graphite source such as graphite, intercalated graphite and nanographite. Exemplary exfoliation methods include, but are not limited to, those practiced in the prior art such as fluorination, acid intercalation, acid intercalation followed by heat shock treatment, and others, or by a combination comprising at least one of the above methods. Exfoliation of nanographite provides a nanographene that has fewer layers than non-exfoliated nanographite. It should be appreciated that the nanographite exfoliation can provide the nanograph as a single sheet of only one molecule in thickness, or as a layered stack of relatively few sheets. In one embodiment, the exfoliated nanographene has less than 50 layers of a single sheet, specifically less than 20 layers of a single sheet, specifically less than 10 layers of a single sheet, and more specifically less than 5 layers of a single sheet.
    [00021] Polysilsesquioxanes, also known as polyorganosilsesquioxanes or polyhydric oligomeric silsesquioxanes derivatives (POSS) are composed of polyorganosilicon oxide of the general formula RSiOi.s (where R is an organic group such as methyl) which has structures of defined closed or open cage (structures jealous or neat). Polysilsesquioxanes, including POSS structures, can be prepared by acid and / or catalyzed condensation based on functionalized silicon-containing monomers such as tetraalkoxy silanes which include tetramethoxy silane and tetraethoxy silane, alkyl trialoxy silanes such as methyltriethoxy silane and methyl trimethoxy silane.
    [00022] Nano-clays can be used in the polymer nanocomposite. The nanoclay may be hydrated or anhydrous silicate minerals with a layered structure and may include, for example, aluminum silicate clay such as kaolins including haliosite, smectites including montmorillonite, illite, and the like. Exemplary nano-clays include those introduced to the market under the trade name CLOISITE® marketed by Souter Clay Additives, Inc. Nano-clays can be exfoliated to separate individual leaves, or they can be exfoliated, and in addition they can be dehydrated or included as hydrated minerals. Other mineral fillers with similarly sized nanotechnology may also be included such as, for example, talc, micas including muscovite, phlogopite, or phengite, or others.
    [00023] Inorganic nanoparticles can also be included in the polymer nanocomposite. Exemplifying inorganic nanoparticles can include a metal or metalloid carbide, such as tungsten carbide, silicon carbide, boron carbide, or yet another; a metal or metalloid nitride, such as titanium nitride, boron nitride, silicon nitride, or yet another; and / or a metal nanoparticle such as iron, tin, titanium, platinum, palladium, cobalt, nickel, vanadium, alloys thereof, or a combination comprising at least one of the above elements.
    [00024] The nanoparticles used herein are derivatized to include functional groups such as, for example, carboxy (e.g., carboxylic acid groups), epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl , alkaryl, lactone, functionalized polymeric or oligomeric groups, or a combination comprising at least one of the above functional groups. The nanoparticles, including the nanograph after exfoliation, are derivatized in order to introduce chemical functionality to the nanoparticle. For example, for the nanographene, the surface and / or the edges of the nanograph sheet are derivatized to increase the dispersibility and interaction with the polymer matrix. In one embodiment, the derivatized nanoparticle can be hydrophilic, hydrophobic, oxophilic, lipophilic, or it can have a combination of these properties to provide a balance of desirable liquid properties, through the use of different functional groups.
    [00025] In one embodiment, the nanoparticle is derivatized, for example, by means of amination to include amine groups, where the amination can be carried out by nitration followed by reduction, or by the nucleophilic substitution of a nucleophile group by an amine, substituted amine, or protected amine, followed by deprotection as needed. In another embodiment, the nanographene can be derivatized by oxidizing methods in order to produce an epoxy, hydroxy or glycol group when using a peroxide, or by cleaving a double bond, for example, a metal-mediated oxidation as a permanganate oxidation to form keto, aldehyde, or functional groups of carboxylic acid.
    [00026] Where the functional groups are alkyl, aryl, aralkyl, alkaryl, functionalized polymeric or oligomeric groups, or a combination of these groups, the functional groups can be joined directly to the nanoparticle derivatized by a carbon-carbon bond without intervention heteroatoms, to provide greater thermal and / or chemical stability to the derivatized nanoparticle, as well as a more efficient synthetic process that requires fewer steps; either by a carbon-oxygen bond (where the nanoparticle contains an oxygen-containing functional group such as hydroxy or carboxylic acid), or by a carbon-nitrogen bond (where the nanoparticle contains a nitrogen-containing functional group such as amine or amide). In one embodiment, the nanoparticle can be derivatized by the metal-mediated reaction with a Ce-30 aryl or a C7-30 aralkyl halide (F, Cl, Br, I) in a carbon-carbon bond formation step, such as by a palladium-mediated reaction such as the Stille reaction, Suzuki coupling, or diazo coupling, or by an organocopper coupling reaction. In another embodiment, a nanoparticle, such as a fullerene, a nanotube, a nanodiamond, or a nanographene, can be directly metallized by reaction, for example, with an alkali metal such as 0 lithium, 0 sodium or 0 potassium, followed by reaction with a cy-30 alkyl or C7-30 alkaryl compound with a nucleophile group such as a halide (Cl, Br, I) or another nucleophile group (eg, tosylate, mesylate, etc.) in one step carbon-carbon formation and bonding. The aryl or aralkyl halide compound, or the alkyl or alkaryl compound, can be substituted by a functional group such as hydroxy, carboxy, ether, or another. Exemplary groups include, for example, hydroxy groups, carboxylic acid groups, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, dodecyl, octa-decyl, and the like; aryl groups including phenyl and hydroxy phenyl; aralkyl groups such as benzyl groups linked through the aryl moiety, such as a 4-methyl phenyl or 4-hydroxy methyl phenyl group, or 4- (2-hydroxyethyl) phenyl (also known as phenethyl alcohol), or an other group further, aralkyl groups attached in the benzyl (alkyl) position as found in a phenyl methyl or 4-hydroxy phenyl methyl group, in position 2 in a phenethyl or 4-hydroxy phenethyl group, or yet another. In an exemplary embodiment, the derivatized nanoparticle is nanographene substituted with a benzyl group, 4-hydroxy benzyl, phenethyl, 4-hydroxy phenethyl, 4-hydroxy methyl phenyl, or 4- (2-hydroxyethyl) phenyl, or a combination comprising at least least one of the groups above.
    [00027] In another embodiment, the nanoparticle can be further derivatized by grafting certain polymer chains to the functional groups. For example, polymer chains such as acrylic chains that have carboxylic acid functional groups, hydroxy functional groups, and / or amine functional groups; polyamines such as polyethylenamine or polyethyleneimine; and poly (alkylene glycols) such as polyl (ethylene glycol) and poly (propylene glycol), can be included by reaction with functional groups.
    [00028] The functional groups of the derivatized nanoparticle can react directly with other components in the polymeric nanocomposite, including the reactive functional groups that may be present in the polymeric or monomeric constituents, leading to increased subjection / reaction of the derivatized nanoparticle with the polymeric matrix. Where the nanoparticle is a carbon-based nanoparticle such as the nanograph, a carbon nanotube, nanodiotherm, or yet another, the degree of derivatization for the nanoparticles can vary from 1 functional group for every five carbon centers to 1 functional group for every 100 carbon centers, depending on the functional group.
    [00029] Nanoparticles can also be mixed with each other, more common particles such as carbon black, mica, clays such as, for example, montmorillonite clays, silicates, fiberglass, carbon fiber, and others, and their combinations.
    [00030] The method of forming the polymer nanocomposite also includes mixing a polymer with the derivatized nanoparticle. The polymer can be any polymer useful for forming a downhole nanocomposite or other applications, and which can be functionalized to form a crosslinkable system (i.e., a thermoset). For example, the polymer may comprise fluoroelastoomers, perfluoroelastomers, hydrogenated nitrile butyl rubber, ethylene propylene diene monomer rubber (EPDM), silicones, epoxy, polyether ketone ether, bismaleimide, polyvinyl alcohol, phenolic resins, polycarbonates , polyesters, polyurethanes, tetrafluoroethylene-propylene elasomeric copolymers, or a combination comprising at least one of the resins above.
    [00031] Exemplary polymers include phenolic resins such as those prepared from phenol, resorcinol, o-, m- and p-xylenol, o-, m- or p-cresol, and still others, and aldehydes such as maldehyde, acetaldehyde, propionaldehyde, butyraldehyde, hexanal, octanal, dodecanal, benzaldehyde, salicylaldehyde, where exemplary phenolic resins include phenol-formaldehyde resins; epoxy resins such as those prepared from bisphenol A diepoxide, polyether ether ketones (PEEK), bismaleimides (BMI), polycarbonates such as bisphenol A polycarbonate, nitrile butyl rubber (NBR), hydrogenated nitrile butyl rubber (HNBR), fluoroelasta rubbers with high fluorine content, such as those in the FKM family and marketed under the trade name VITON® (available from FKM-Industries) and perfluoroelastomers such as FFKM (also available from FKM -Industries) and also marketed under the perfluoroelastomer trademarks KALREZ® (available from DuPont), and VECTOR® adhesives (available from Dexco LP), organopolysiloxanes such as functionalized or non-functionalized polydimethyl siloxanes (PDMS), elastomeric copolymers of tetrafluoroethylene-propylene such as those marketed under the trademark AFLAS® and marketed by Asahi Glass Co., ethylene-propylene-d monomer rubbers yen (EPDM), polyvinyl alcohol (PVA), and others. The combinations of these polymers can also be used.
    [00032] In one embodiment, the polymer can be a polyurethane resin. Polyurethanes in general are condensation products of a di- or polyisocyanate and di- or polyhydroxy compound. A chain extender, for example, those based on di- or polyamines, can alternatively or additionally be included in place of all or part of the diol filler to form the polymer composition.
    [00033] Di- and polyhydroxy compounds can include, for example, diols and polyols having 2 to 30 carbon atoms. Useful diols may include glycols including oligomeric glycols that have alkoxy repeat units including di-, tri- and higher glycols, or polyglycols. Exemplifying diols may include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butane diol, 1,4-butane diol, bis-hydroxy methyl cyclohexane, neopentyl glycol, dietary lene glycol, hexane diol, dipropylene glycol, tripropylene glycol, polypropylene glycol, triethylene glycol, polyethylene glycol, oligomeric and polymeric tetraethylene glycols such as polyethylene glycols, polypropylene glycols, polybutylene glycols, poly (ethylene propylene) glycols , and still others. Combinations comprising at least one of the above dihydroxy compounds can be used.
    [00034] Suitable exemplifying polyols include triols, for example, glycerol, trimethylol propane, pentaerythritol, tris (2-hydroxyethyl) isocyanurate, and the like; tetrols such as dipentaerythritol; and other sugar alcohols such as inositol, myoinositol, sorbitol, and others. Combinations comprising at least one of the above polyhydroxy compounds can be used.
    [00035] Polyurethanes are typically prepared by condensing precursor components of a diisocyanate with a diol and / or a diamine. It should be appreciated that, where a polyol is included, a cross-linked polyurethane is formed. Aliphatic polyurethanes having at least two urethane portions per repeating unit are useful, wherein the diisocyanate and diol used in the preparation of the polyurethane comprise divalent aliphatic groups which may be the same or different. The divalent aliphatic units can be from C2 to C30, specifically from C3 to C25, more specifically the alkylene groups from C4 to C20, including straight chain alkylene, branched chain alkylene, cycloalkylene, heteroalkylene such as oxyalkylene (including polyethylene alkylene) ), and others. Exemplary aliphatic diradical groups include, but are not limited to, ethylene; 1,2- and 1,3-propylene; 1.2 -, 1.3 -, and I, 4-butylene; 1,5-pentamethylene; 1,3- (2,2-dimethyl) propylene; 1,6-hexamethylene; 1,8-octamethylene; 1,5- (2,2,4-trimethyl) pentylene, 1,9-nonamethylene; 1,6- (2,2,4-trimethyl) hexylene; 1,2-, 1,3- and 1,4-cyclohexylene; 1,4-dimethylene cyclohexane; 1,4-undecamethylene; 1,12-dodecamethylene, and others.
    [00036] Monomeric diisocyanates can be used in the preparation of polyurethane. The diisocyanate component may be a C4-20 aliphatic or aromatic C4-20 monomeric diisocyanate. Exemplary aliphatic diisocyanates include isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; 1,4-tetramethylene diisocyanate; 1,5-pentamethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,7-heptamethylene diisocyanate; 1,8-octamethylene diisocyanate; 1,9-nonamethylene diisocyanate; 1.10-decamethylene diisocyanate; 2,2,4-trimethyl-1,5-pentamethylene diisocyanate; 2,2'-dimethyl-1,5-pentamethylene diisocyanate; 3-methoxy-1,6-hexamethylene diisocyanate; 3-butoxy-1,6-hexamethylene diisocyanate; omega, omega, omega'-dipropyl ether diisocyanate; 1,4-cyclohexyl diisocyanate; 1,3-cyclohexyl diisocyanate; trimethylhexamethylene diisocyanate; and combinations that comprise at least one of the above elements.
    [00037] Exemplary aromatic polyisocyanates include toluene diisocyanate, methylene bis-phenylisocyanate (diphenylmethane diisocyanate), methylene bis-cyclohexylisocyanate (hydrogenated MDI), naphthalene diisocyanate, and still others.
    [00038] Polymeric or oligomeric diisocyanates can be used additionally or alternatively in the preparation of a polyurethane, or a copolymer bound with urethane or urea. Exemplary oligomeric or polymeric chains for polymeric diisocyanates include polyurethanes, polyethers, polyester, polycarbonate, polyester carbonates, and others. In one embodiment, the polyisocyanate is a polymeric polyisocyanate, such as a polymer chain with isocyanate end groups. Useful polyisocyanates include those based on polyesters such as polyaliphatic esters that include polylactones, polyarylate esters that include phthalate copolymers with phenols such as bisphenol A, dihydroxy benzenes, and the like; and polyesters (aliphatic-aromatics) such as ethylene terephthalate, butylene terephthalate, and others.
    [00039] A useful class of diisocyanates based on polyaliphatic esters is based on polylactones such as polybutyrolactones, polycapractactones, and others. Exemplary polyester diisocyanates based on these polyesters include ADIPRENE® LFP 2950A and PP 1096, available from Chemtura, which are polylprolactone prepolymers terminated in p-phenylene diisocyanate (PPDI). Thus, in a specific embodiment, the polymer can be a polyurethane, a polyester bonded with urethane, or a polyester bonded with urea.
    [00040] Alternatively or in addition to a dihydroxy compound, the diisocyanate can be condensed with a diamine, sometimes indicated as a chain extender. It should be appreciated that the condensation of a diisocyanate with a dihydroxy compound produces a bond of the urethane in the polymer backbone, whereas the condensation of the diisocyanate with the diamine produces a urea bond in the polymer backbone. Exemplary chain extenders include C4-30 diamines. Diamines can be aliphatic or aromatic. In a specific embodiment, useful diamines include aromatic diamines such as, for example, 4,4'-bis (aminophenyl) methane, 3,3'-dichloro-4,4'-diaminodiphenyl methane (also known as 4.4 ' -methylene-bis (o-chloroaniline), abbreviated by MOCA), dimethyl sulfide toluene diamine (DADMT), and others.
    [00041] Where a polyurethane, a urethane-bound polyester, or a urea-bound polyester is formed, the formation of these polymers can be accomplished by combining as a precursor a composite that has at least two isocyanate groups, and a polyol, a diamine, or a combination comprising at least one of the above elements. In one embodiment, the composite having at least two isocyanate and polyol and / or diamine groups is mixed simultaneously. In another embodiment, the composite having at least two isocyanate and polyol groups, diamine, or a combination of these are added sequentially.
    [00042] The nanoparticle can be formulated as a solution or dispersion and be cast or coated, or it can be mechanically dispersed in a polymer resin matrix. Mixing and dispersing the nanocharge and polymer resin can be carried out by methods such as, for example, extrusion, high shear mixing, rotary mixing, three roller mixing, and others. The properties of the polymer nanocomposite can be adjusted by selecting the nanocharge; for example, the derivatized plate-type nanographene can be arranged or assembled into the composite by taking advantage of the nanographene's intrinsic surface properties after exfoliation, in addition to the functional groups introduced by derivatization.
    [00043] In the polymer nanocomposite, nanoparticles can be present in an amount of 0.01 to 30% by weight, specifically from 0.05 to 27% by weight, more specifically from 0.1 to 25% by weight, more specifically from 0.25 to 22% by weight, and even more specifically from 0.5 to 20% by weight, based on the total weight of the polymer nanocomposite.
    [00044] In a specific embodiment, a method for forming a polymer composite comprises mixing a polymer, and from 0.5 to 20% by weight of a derivatized nanoparticle based on the total weight of the polymer composite, in whereas the derivatized nanoparticle includes functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaline, lactone, functionalized polymeric or oligomeric groups, or a combination comprising at least one of the functional groups above.
    [00045] The polymer nanocomposite has less variation in the measured properties than can be obtained where an identical, but not derivatized, na-noparticle is used. In addition, the variation in the percentage of elongation measured, at the tensile strength limit, or at both the elongation and the tensile strength limit for the polymer nanocomposite is less than or equal to 5%.
    [00046] The polymer and derivatized nanoparticle can be formed as a dispersion to facilitate processing. The solvent can be an inorganic solvent such as water, including deionized water, or protected or buffered or pH-adjusted water, mineral acid, or a combination comprising at least one of the above elements, or an organic solvent comprising an alkane, alcohol, ketone, oils, ethers, amides, sulfones, sulfoxides, or a combination comprising at least one of the above elements.
    [00047] Exemplary inorganic solvents include water, sulfuric acid, hydrochloric acid, or yet another; exemplifying oils include mineral oil, silicone oil, or yet another; and exemplifying organic solvents include alkanes such as hexane, heptane, 2,2,4-trimethyl pentane, n-octane, cyclohexane, and the like; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, octanol, cyclohexanol, ethylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, and others; ketones such as acetone, methyl ethyl ketoin, cyclohexanone methyl ether ketone, 2-heptanone, and others; esters such as ethyl acetate, propylene glycol methyl ether acetate, ethyl lactate, and others; ethers such as tetrahydrofuran, dioxane, and the like; polar aprotic solvents such as N, N-dimethylformamide, N-methyl caprolactam, N-methyl pyrrolidine, dimethyl sulfoxide, gamma-butyrolactone, or yet another; or a combination comprising at least one of the above elements.
    [00048] Uniform (homogeneous) mixing to prevent gel formation is desirable in formulations of reactive polymers or resins such as, for example, in the formation of polyurethanes from the polyol-polyisocyanate reaction. Inhomogeneous mixing can trap air bubbles, which causes mixing density and spatial variation, and causes variation in the chemical composition of the formulation, which can also cause variations in properties.
    [00049] Uniform mixing and dispersion can be enhanced by the presence of specialized additives. Such additives include dispersants that have olefinic, fluoridated, acidic or acid-derived functionality. Nanoparticles and other fillers have been included in polymers to enhance mechanical properties including temperature-based mechanical properties, such as impact resistance. In particular, carbon-based nanoparticles with a large surface area such as, for example, graphene, nanotubes, and others, may have a high surface activity. However, common dispersants may not sufficiently disperse fillers or other suspended particles in a composite. However, it has been surprisingly found that derivatized nanoparticles, such as derivatized nanographene, act as dispersion aids in polymer nanocomposites, which is not achieved when using non-derivatized nanoparticles with or without dispersants. It was found that the use of nanoparticles alone, including carbon-based nanoparticles, increases variability and decreases the quality of the mixture, while the use of derivatized nanoparticles reduces variability and increases the quality of the mixture.
    [00050] The polymer, the derivatized nanoparticle, and any solvent can, therefore, be combined by means of extrusion, high shear mixing, three roller mixing, rotary mixing, or solution mixing. In a specific embodiment, the mixture produces a uniform homogeneous mixture for the polymer nanocomposites that are being prepared. In an exemplary embodiment, where a polyurethane dispersion is prepared, the dispersion can be combined and mixed in a rotary mixer, or by a continuous flow reactive mixing method such as a reactive injection molding (RIM) process.
    [00051] Rotary mixing is a method of mixing in which the vessel containing the components of the mixing is rotated around its axis, while simultaneously processing in a fixed radius around a second center of rotation. Mixing in this way provides a high shear and the elimination of bubbles, while avoiding the use of agitators that can lead to an inhomogeneous composition that can be caused, for example, by different mixing zones within the mixing vessel, and bubbles generated by mixing and cavitation. The use of vacuum in processing can further improve both mechanical properties and (reduced) variability by removing volatile components and any adventitious bubbles that may form during the mixing process. An example of a rotary mixer that can provide an appropriate mix of components (ie, polymer and derivatized nanoparticle), with or without vacuum, is a Totational Vacuum Mixer AR 310 THINKY® (available from Thinky, Inc.).
    [00052] Mixing by a rotary injection molding type process can be performed using two or more continuous feed streams, where the derivatized nanoparticle can be included as a component of one of the feed streams (for example, where the polymer is a polyurethane prepared by using different feed streams, the derivatized nanoparticle is included in the diisocyanate or polyol streams, diamine, etc., or in a separate stream as a suspension in a solvent). Mixing in such systems is carried out by the flow within the mixing zone at the point of introduction of the components.
    [00053] In one embodiment, the derivatized nanoparticle is mixed with the thermoset polymer precursor (s) simultaneously with the initiation of the thermoconsolidation reaction. In another embodiment, the derivatized nanoparticle is introduced after the thermoconsolidation reaction is initiated. In one embodiment, the derivatized nanoparticle is mixed with the thermoset polymer precursor (s) before a two-fold increase in the viscosity of the mixture, where the inclusion of the derivatized nanoparticle before the increase in viscosity ensures uniform dispersion of the nanoparticle derivatized.
    [00054] It has been found that homogeneous mixtures (ie nanocomposites) of nanoparticles derivatized with polymers, formed by rotary mixing, have less variability in the limit of tensile strength and elongation for any combination of nanoparticles and polymer. "Variability", as discussed here, means the difference between the maximum and the minimum in the measured values for different physical properties, for any sample in question. Surprisingly, the use of derivatized nanoparticles reduces this variability, while increasing the mechanical properties for composites formed by this method. In one embodiment, where a derivatized nanoparticle is mixed with the polymer under rotational mixing conditions, the variability in physical properties, including limits of tensile strength and the percentage of elongation (% elongation), is less than the variability obtained where the non-derivatized nanoparticle is used.
    [00055] In one embodiment, the relative variability in physical properties (expressed as a percentage), such as% elongation and the tensile strength limit, is less than or equal to ± 2.0%, specifically less than than or equal to ± 1.5%, more specifically less than or equal to ± 1.0% and even more specifically less than or equal to ± 0.5%. In a specific embodiment, the absolute variability in the limit of tensile strength is less than or equal to ± 200 MPa, specifically less than or equal to ± 150 MPa, more specifically less than or equal to ± 100 MPa and even more specifically less than or equal to ± 75 MPa. Also in a specific modality, the absolute variability in the percentage of elongation is less than or equal to ± 25%, specifically less than or equal to ± 20%, more specifically less than or equal to ± 10% and even more specifically less than or equal to ± 5%. In another embodiment, the homogeneous mixing of the polymer and the derivatized nanoparticle is carried out by a low-shear mixture such as, for example, rotary mixing. Derivatized nanoparticles are thus used effectively as formulation additives for homogeneous final parts made from reactive formulations such as those based on polyurethane, rubber, and others.
    [00056] Derivatized nanoparticles are thus used effectively as formulation additives for homogeneous final parts made from reactive formulations such as those based on polyurethane, rubber, and others. The load of these nanoparticles varies from 0.01% by weight to 30% by weight, where it has been found in exemplifying systems that the amounts of less than or equal to 1% by weight are sufficient to improve properties such as the limit of resistance to traction and elongation by 5% or more. To improve mixing, the polymer and derivatized nanoparticle can be dispersed in a solvent that includes inorganic solvents such as water, or mineral acids such as sulfuric acid, or organic solvents that include oils, alcohols and glycols, ketones such as methyl ethyl ketone (MEK), ethers such as tetrahydrofuran (TF), polar aprotic solvents such as N, N-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and other solvents.
    [00057] During dispersion, the inclusion of derivatized nanoparticles can help in mixing and molding systems for laminar and / or turbulent flow. In these systems, the nanoparticle, the derivatized polymer and the relative charges, plus the use of the added solvent, can be selected in order to provide a Reynolds number for compositions other than 0.001 to 1000. These Reynolds number values can be obtained for mixing the components for the polymer nanocomposite, when mixing with or without vacuum.
    [00058] In another embodiment, a method for forming a polymer composite comprises derivatizing a nanoparticle to include functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactone, functionalized polymeric or oligomeric groups, or a combination comprising at least one of the above functional groups, and mixing the derivatized nanoparticle with a polymer by means of rotary mixing.
    [00059] In a specific embodiment, a method for forming a polyurethane nanocomposite comprises derivatizing a nanoparticle to include functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactone, functionalized polymeric or oligomeric groups, or a combination comprising at least one of the above functional groups, and mixing by rotary mixing of 0.05 to 20% by weight of the derivatized nanoparticle, with a polyurethane, a urethane-bound polyester, or a urea-bound polyester that comprises a composite that has at least two isocyanate groups, a polyol, a diamine, or a combination of these, in which the amount of derivatized nanoparticle is based on the total weight of the nanocomposite of polyurethane.
    [00060] The articles can be formed from the polymer nanocomposite prepared by the method above. Due to the fact that the polymer nanocomposites of the invention have few mechanical defects in the mixing process, articles prepared from polymer nanocomposites will have better mechanical properties, reliability and environmental stability. Thus, in one embodiment, an article comprises the polymer nanocomposite. The polymer nanocomposite can be used to form all or part of an article.
    [00061] The article can be useful for a downhole application such as, for example, a compacting element, an eruption preventive control element, a torsion spring for a safety valve under the surface, an engine protection bag submersible pump, an eruption preventive control element, a sensor guard, a pumping rod, an O-ring, a T-ring, a gasket, a pumping rod seal, a pump shaft seal, a seal pipe, a valve seal, a seal for an electrical component, an insulator for an electrical component, a seal for a drill motor, or a seal for a drill bit. EXAMPLES
    [00062] Preparation of Derivatized Nanographene. Nanographite (200 mg, with an average particle size (diameter) of about 1 to 1.5 pm, marketed as XGn nanographite, available from XG Sciences) is suspended in 200 ml of liquid ammonia in a dry ice bath / acetone. The lithium metal (480 mg) is added to the liquid ammonia solution, with which the solution reaches a blue color that indicates the dissolution of lithium. When the addition of lithium is completed, the solution is stirred for 30 minutes, and 4-phenethyl alcohol (p-Br- (CeH5) -CH2CH2OH) (13.4 g) is then added slowly to the reaction mixture. The resulting solution is put to react for four hours at room temperature, after which the ammonia is removed slowly to isolate the solid product. The resulting solid material is isolated to obtain nanographene derivatized with p-phenethyl alcohol. This exfoliation / derivatization of the nanographite is illustrated in FIG 1. FIG. 2 is a photograph showing a comparison of freshly prepared suspensions of nanographite (FIG. 2A) in dimethyl formamide (DMF), and the derivatized nanographene (FIG. 2B) in DMF (derivatized with p-phenethyl alcohol groups), where demonstrates that the derivatized nanographs remain suspended after the nanographite has sedimented out of the solution.
    [00063] Preparation of Polymer Nanocomposites. A series of polymer nanocomposites was prepared from a prepolymer terminated with p-phenyl isocyanate based on polycarprolactone (marketed as ADIPRENE® 2950A, available from Chemtura) and a chain extender (diamine MOCA; marketed; as VIBRACURE® A 133, and available from Chemtura), ethyl methyl ketone as a solvent, and combined with nanoparticles including Cloisite® 30B Nano-clay (available from Southern Clay Additives, Inc.), XGn platelet-type nanograph (available from XG Sciences ), or functionalized nanographite, prepared as described herein. All mixing was performed using a THINKY® rotary vacuum mixer, AR model 310 (available from Thinky, Inc.). The physical variables that affect the compositions were studied, including the nanoparticle load (0, 1.0, 2.5 or 5.0% by weight based on the total weight of the nanoparticle (abbreviated as NP), the prepolymer and chain extender), mixing time, application or absence of vacuum during processing. The polymer compositions were shaped as sheets that are 2 mm thick, and tested for physical parameters including the modulus of elasticity (in megapascals, abbreviated as MPa), the tensile strength limit (MPa) and the elongation under tension (%), each determined according to a standard method (ASTM D638).
    [00064] Comparative Examples 1-18 and Example 1 were prepared by using the prepolymer and the chain extender above in the following amounts, and by using mixing times and applying vacuum, as follows:
    [00065] Comparative Examples 1-18 and Example 1 above were then formed as sheets and samples (in triplicate) were tested for tensile strength, elongation and modulus properties (100% modulus and 300%). The data are summarized in Table 2, below. Table 2
    [00066] Table 2 shows the data for the limit of tensile strength, the% elongation, the modulus of 100% and 300%, and the average modulus (that is, the average of the modules of 100% and 300 %) for each of Comparative Examples (CEx.) 1-18 and for Example (Ex.) 1 (derivatized nanographene). The samples for each of the examples and the comparative example were evaluated in triplicate (samples # 1 to # 3). As can be seen in the detailed data summarized in Table 2, the variability between each of the three samples for each example and the comparative example, and the difference between the mean values, can be significant. To determine the significance of the differences between these samples, the data were analyzed using the MINITAB® Statistical Analysis Software for statistical analysis, available from MINITAB, Inc.
    [00067] Statistical Analysis of Process Variables for Controls (CEx. 1-3) and Comparative Examples (CEx. 4-18). Process variables including mixing time and vacuum application were statistically assessed for comparative examples for each nanoparticle evaluated.
    [00068] The mean variability for all Comparative Examples 1-18 and Example 1 was obtained by calculating the maximum variability for each comparative example or example of the mean of the three samples for each of the CEx. 1-18 and Ex. 1, based on the maximum deviation from the mean value for each for each comparative example or example as a deviation from the mean value. In this way, the average variability was determined from each of 19 molded plates (which correspond to the polymer nanocomposites of CEx. 1-18 and Ex. 1) at three data points (samples) per plate. The average variability is shown in Table 3, below: Table 3
    [00069] The resulting average variability represents the combined inherent variability for mixing, for the molding process, and for the property measurement technique. As seen in Table 3, the average variability is the highest for the limit of tensile strength at 12.1%, followed by the percentage of elongation at 9.7%. The variation in the module, at 100 and 300%, is the smallest at 2.5% and 2.7% respectively.
    [00070] FIG. 3 shows a graph of the control samples (CEx. 1-3) for the% elongation (FIG. 3A) and the tensile strength limit (FIG. 3B). As seen in the attached graphs, the values for the% of average elongation and the tensile strength limit show a tendency to increase the CEx. 1 (Control 1) to CEx. 3 (Control 3). However, also as seen in the graphs, the CEx data. 1 are statistically significantly smaller than each of the CEx. 2 and 3, which are not statistically different from each other (p = 0.122 for the limit of tensile strength and p = 0.288 for stretching).
    [00071] FIG. 4 shows graphs of the tensile strength limit (FIG. 4A), the% elongation (FIG. 4B) and the average modulus (mean values of 100% and 300% modules; Fig. 4C) for nanocomposites of charged polymers with nano clay at mixing times of 5 minutes (CEx. 4-7) and 30 minutes (CEx. 8-11). In the figures, it can be seen that the mean values of the tensile strength limit increase by 33% (FIG. 4A), by 4.2% for the stretching (FIG. 4B), and by 12.7% for the module mean (FIG. 4C), but that the increase in elongation was not statistically significant (p = 0.287 in FIG. 4B) whereas increases in the tensile strength limit (p = 0.004 in FIG. 4A) and the mean modulus (p = 0.000 in FIG. 4C) were statistically significant.
    [00072] FIG. 5 shows graphs of the tensile strength limit (FIG. 5A), the% elongation (FIG. 5B) and the average module (average values of the 100% and 300% modules; FIG. 5C) for the nanocomposites of polymers loaded with nano clay without vacuum processing (CEx. 4 and 5) and with vacuum processing (CEx. 6 and 7). In the figures, it can be seen that the mean values of the tensile strength limit increase by 96% (FIG. 5A), by 32% for the elongation (FIG. 5B), and by 16.3% for the average module ( FIG. 5C). In addition, increases in the tensile strength limit, elongation and mean modulus were statistically significant in all comparative examples (p = 0.012 in FIG. 5A; p = 0.012 in FIG. 5B; p = 0.001 in FIG. 5C ).
    [00073] FIG. 6 shows graphs of the tensile strength limit (FIG. 6A), the% elongation (FIG. 6B) and the average module (average values of the 100% and 300% modules; Fig. 6C) for the nanocomposites of polymers loaded with nanographite (XGn) at mixing times of 5 minutes (CEx. 13, 15, 17) and 30 minutes (CEx. 14, 16, 18). In the figures, it can be seen that the mean values of the tensile strength limit decrease by 5.5% (FIG. 6A), by 5.1% for the stretch (FIG. 6B), and marginally increase by 0.8 % for the average module (FIG. 6C). Unlike the nano clay load data in FIGs. 4A-4C, the variability for the measured tensile strength limit and elongation increased with the longer mixing time, whereas the variability in the modulus decreased slightly; however, the decreases were not significantly different in the tensile strength limit (p = 0.554 in FIG. 6A) and in the elongation (p = 0.370 in FIG. 6B) whereas increases in the tensile strength limit (p = 0.049 in FIG. 6C) were marginal but statistically insignificant.
    [00074] FIG. 7 shows graphs of the tensile strength limit (FIG. 7A), the% elongation (FIG. 7B) and the average module (average values of the 100% and 300% modules; Fig. 7C) for charged polymer nanocomposites with nanographite without vacuum processing (CEx. 13 and 14) and with vacuum processing (CEx. 15 and 16). In the figures, the average values decrease for the limit of tensile strength by 5.3% (FIG. 7A), and by 1.7% for the elongation (FIG. 7B), but increase by 1.2% for the module medium (FIG. 7C). Changes in the tensile strength limit, elongation and mean modulus were not statistically significant in all comparative examples (p = 0.571 in FIG. 7A; p = 0.741 in FIG. 7B; p = 0.197 in FIG. 7C); however, it can be seen that the variability decreases in all cases with the use of vacuum, thus providing a more consistent result.
    [00075] Nanoparticle Load Assessment. The analysis of data for the load of nanoparticles for each type of composition based on nanoparticles (nano-clay (CEx. 4-11), on nanographite (CEx. 12-18), and the comparison of 1% by weight of nanographite (CEx. 12) with 0.9% by weight of derivatized nanographene (Ex. 1) are shown in FIGS. 8-10 below, and data comparisons for the different nanoparticles for each measured property (tensile strength limit, elongation , and mean modulus based on the mean values of the 100% and 300% modulus) are shown in FIGS. 11-13, with another cross plot of the sample means that compare the percentage of elongation for the modulus (FIG. 14) Each compositional point (x-axis) in FIGURES 8-10 includes all data points for the triplicate samples, and the average data point is calculated from them. Error bars are included for the mean data, representing 95% confidence intervals based on the observed variability determined at from sample analysis and variability as discussed above. For all comparisons in FIGURES 8-10, the values of the mean modulus, the tensile strength limit, and the elongation for Comparative Example 3 of the control were adjusted as baseline values.
    [00076] FIG. 8 shows the effect of loading on the tensile strength limit (FIG. 8A), elongation (FIG. 8B) and module (FIG. 8C) for Comparative Examples 4-11 containing nano-clay, and Comparative Example 3 for control . As seen in the graph of the average data points, FIG. 8A shows a slight decrease in a tensile strength limit of 5.1% compared to the control (CEx. 3), since the nano clay load is increased to 2.5% by weight and to 5% by weight. Similarly, FIG. 8B shows a slight decrease in a tensile strength limit of 2.6% compared to the control (CEx. 3) as the nano clay load is increased to 2.5% by weight and to 5% by weight. These decreases in FIGs. 8A and 8B are not statistically significant. In FIG. 8C, however, the average modulus increases by 8% statistically significant since the nano-clay is increased from 0 to 2.5% by weight, and by 5.8% statistically significant since the nano-clay is increased from 0 to 5 , 0% by weight, where it is also seen that additional increases in the levels of nano clay from 2.5% by weight to 5.0% by weight result in an apparent decrease in the mean modulus, which is not statistically significant. Therefore, the presence of nano-clay improves the modulus, but not other properties, such as the limit of tensile strength and elongation.
    [00077] FIG. 9 shows the effect of load on the tensile strength limit (FIG. 9A), elongation (FIG. 9B) and module (FIG. 9C) for Comparative Examples 12-18 that contain nanographite (XGn), and Examples Comparatives 1-3 of control. As seen in the graph of the average data points, FIG. 8A shows a statistically significant total decrease in the tensile strength limit of 36% (at 5.0% by weight of nanographite) compared to the control (CEx. 3) since the nanographite load is increased from 0 to 1, 0% by weight, 2.5% by weight and 5% by weight. Although a decrease of up to 12.6% by weight to 2.5% by weight of nanographite charge, the decrease is only statistically significant between 2.5% by weight and 5.0% by weight of nanographite. Similarly, FIG. 8B shows a 15.6% decrease in elongation compared to the control (CEx. 3) since the nanographite load is increased from 0% by weight to 5.0% by weight. No decrease in elongation is observed essentially until a nanographite load of 2.5% by weight, where in a trend similar to that seen for the limit of tensile strength, the decrease in elongation becomes pronounced, albeit marginally and not statistically between 2.5% by weight and 5.0% by weight of nanographite. In FIG. 8C, however, the average modulus increases by 8% statistically significant since the nano-clay is increased from 0 to 2.5% by weight, and by 11.7% statistically significant by 1% by weight, and 9, 6% for a load of 5.0% by weight of the nanographite. However, increasing the nanographite levels from 1.0% by weight to 5.0% by weight does not result in any further increase in the average module; all values for these loads are not statistically different. Therefore, the presence of nanographite improves the modulus, but not other properties, such as the limit of tensile strength and elongation.
    [00078] FIG. 10 shows the effect of load on the tensile strength limit (FIG. 10A), elongation (FIG. 10B) and module (FIG. 10C) for Comparative Example 12 which contains 1% by weight of nanographite (XGn), and Comparative Examples 1-3 of control, versus Example 1 which contains 0.9% by weight of nanographene derivatized with phenethyl alcohol (Fnl_Gn). As seen in the graph of the average data points, FIG. 10A shows no increase in the tensile strength limit with the inclusion of 1% by weight of XGn compared to the control, but an increase in the tensile strength limit of 18% with the inclusion of 0.9% in weight of Fnl_Gn in relation to what is marginally statistically significant in relation to the control (CEx. 3). The increase is, however, statistically significant between XGn and Fnl_Gn, and the variability of the derivatized nanoparticle Fnl_Gn in the 95% confidence interval is significantly less than that of the control and non-derivatized XGn. FIG. 10B shows a slight increase, but statistically insignificant at a 3% elongation compared to the control (CEx. 3) for the 0.9% by weight de-rivatized nanographene Fnl_Gn; the increase in elongation is not statistically significant in relation to the non-derivatized nanographite (XGn) particle. Thus, there is essentially no change in elongation for either nanoparticle; however, the variability of the derivatized nanoparticle Fnl_Gn in the 95% confidence interval is significantly less than that of the control and non-derivatized XGn. In FIG. 10C, the average module increases by 11.7% statistically significant for XGn and by 12.8% for Fnl_Gn, in relation to the control. However, the variability in the module also increases for XGn and Fnl_Gn in relation to the control, and therefore there is no statistical difference between the modules for XGn and Fnl_Gn. Therefore, the use of derivatized nanographene improves the limit of tensile strength compared to non-derivatized nanographite, and significantly reduces the variability in the limit of tensile strength and elongation although the mean modulus is statistically the same for XGn and Fnl_Gn.
    [00079] FIG. 11 summarizes the values of the tensile strength limit for control 2 (CEx. 2), control 3 (CEx. 3), 2.5% by weight of nano-clay (CEx. 8), 5% by weight of nano-clay ( CEx. 9), 2.5% by weight of XGn (CEx. 17), 5% by weight of XGn (CEx. 18), and nanographene derivatized with phenethyl alcohol (Fnl_Grafene; Ex. 1). In the figure, it can be clearly seen (in relation to control 3) that a tendency to decrease the limit of tensile strength is observed for 2.5% by weight of nano-clay, 5% by weight of nano-clay, 2.5 % by weight of nanographite, and 5% by weight of nanographite, but that a significant increase of 17.8% in the limit of tensile strength is observed for the nanographene derivatized with phenethyl alcohol (Ex. 1) even at a lower load of 0.9% by weight.
    [00080] In addition, the variation in the limit of tensile strength is much smaller for the nanographene derivatized with phenethyl alcohol from Ex. 1 than for any of the controls or comparative examples.
    [00081] FIG. 12 summarizes the values of% elongation for control 2 (CEx. 2), control 3 (CEx. 3), 2.5% by weight of nano-clay (CEx. 8), 5% by weight of nano-clay (CEx. 9), 2.5% by weight of XGn (CEx. 17), 5% by weight of XGn (CEx. 18), and nanographene derivatized with phenethyl alcohol (Fnl_Gn; Ex. 1). In the figure, there is no statistical difference between control 3 (CEx. 3) and any of the other comparative examples or Ex. 1, except that the value of 5% by weight for the tendency to decrease the tensile strength limit is observed for 2.5% by weight of nano-clay, 5% by weight of nano-clay, 2.5% by weight of nanographite, and 5% by weight of nanographite, but that a significant increase of 17.8% in the limit tensile strength is observed for the nanographene derivatized with phenethyl alcohol (Ex. 1) even at a load less than 0.9% by weight. In addition, the variation in the tensile strength limit is much smaller for the nanographene derivatized from Ex. 1 than for any of the controls or comparative examples.
    [00082] FIG. 13 summarizes the average values of the module for control 2 (CEx. 2), control 3 (CEx. 3), 2.5% by weight of nano-clay (CEx. 8), 5% by weight of nano-clay (CEx. 9 ), 2.5% by weight of XGn (CEx. 17), 5% by weight of XGn (CEx. 18), and nanographene derivatized with phenethyl alcohol (Fnl-Gn; Ex. 1). In the figure, a general tendency to increase the modulus is observed for the progression of control 3, 2.5 wt.% And 5 wt.% Of nano-clay (noting that 5.0 wt. the 2.5% by weight of nano-clay, but that these compositions are not statistically different), 2.5% by weight of XGn, 5.0% by weight of XGn, and derivatized nanographene (noting that there is no statistical difference between the derivatized nanographene (Fnl_Gn) and the 5% by weight of XGn. The derivatized nanographene has an average module 12.8% greater than that of control 3 (CEx.3) even at a low load of 0.9% in weight, however, the variability of derivatized nanographene is greater than that of non-derivatized nanographite and comparable to that of nano-clay.
    [00083] FIG. 14 summarizes the data in FIGURES 11 and 12, tracing the data to show the net effect of using derivatized nanographene (Fnl_Gn) in relation to non-derivatized nano-clay or nanographite (XGn). The graph emphasizes the fact that derivatized nanographene has a combination of properties that are greater than those of non-derivatized nanoparticles. Derivatized nanographene has a longer average elongation compared to all comparative examples, and although not statistically greater than control 3, 2.5 wt% XGn and 2.5 wt% nano clay, the variability is much less ; in particular, as seen in the error bars in FIG. 14, for 0.9% by weight of Fnl_XGn, the variability in the% of elongation is ± 4.25%, whereas the variability for Control 3, 2.5% by weight of XGn, and 2.5% by weight of nano-clay samples are ± 74.7%, ± 85.5%, and ± 28.3%, respectively. This translates into a relative variability of ± 0.27% for Fnl_XGn, which is significantly less than the next closest comparative example of 2.5% by weight of nano-clay to ± 3.05%. The limit of tensile strength is also greater than that observed in the comparative examples and with much less variability; in particular, as seen in the error bars in FIG. 14, for 0.9% by weight of Fnl_XGn, the variability in the limit of tensile strength is ± 70 MPa, whereas the variability for Control 3, 2.5% by weight of XGn, and 2.5% by weight of nano-clay samples, it is ± 435 MPa, ± 753 MPa and ± 211 MPa, respectively. This translates into a relative variability of ± 0.39% for Fnl_XGn, which is significantly less than the next closest comparative example of 2.5% by weight of nano-clay at ± 2.66%. The significantly reduced variability in these properties in the derivatized nanographene demonstrates that a polymer nanocomposite that incorporates derivatized nanoparticles, and in particular the derivatized nanograph, and when combined with a polyurethane matrix when using rotary mixing, exhibit improved properties and less variability (and hence greater process control) than can be achieved when non-derivatized nanoparticles are used, even when other parameters such as test error, intrinsic mixing variability, particle loading, and the use of vacuum processing are used. taken into account in the data.
    [00084] Furthermore, FIG. 15 shows a graph of stress (in pounds per square inch) versus strain (%) for CEx samples. 3 (duplicate runs A and B) and for Ex. 1 (duplicate runs A and B). The graph shows an increasing tension with increasing deformation, indicative of the increased (increased) deformation hardening, for the composition of Example 1 in relation to that of Comparative Example 3 of control.
    [00085] Thus, to summarize, longer mixing times (for example, 30 minutes) and the addition of a solvent (MEK) improves the dispersion of nanoparticles in polyurethane formulations, which improves the mechanical performance of the polymer nanocomposite (for example, the tensile strength limit and elongation). Nano clay generally exhibits better dispersion than XGn graphite nanoplatforms; however, quantities as small as 0.9% by weight of nanographene derivatized with phenethyl alcohol groups provided a greater improvement in performance at a higher tensile strength limit of about 18%, a higher elongation of about 3%, and a higher modulus of about 13% when compared to a polymeric control without load (polyurethane). In addition, the inclusion of derivatized nanographene reduces the statistical variation in the measured properties of both the tensile strength limit and the percentage of elongation, indicative of good dispersion and positive interaction with a polymer matrix. In this way, functionalized graphene can be used as a dispersion aid in polymers including urethane or urea-bound polyesters.
    [00086] Although one or more modalities have been shown and described, modifications and substitutions can be made in them without deviating from the character and scope of the invention. Therefore, it should be understood that the present invention has been described by way of illustration and not by way of limitation.
    [00087] This written description uses examples to present the invention, including the best mode, and also to allow any element skilled in the art to design and use the invention.
    [00088] The patentable scope of the invention is defined by the claims, and may include other examples that occur to elements skilled in the art. Such other examples are apt to fall within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with non-substantial differences from the literal language of the claims.
    [00089] All ranges indicated here are inclusive of the end points, and the end points are independently combinable with each other. The suffix "(s)" as used herein lends itself to include both the singular and the plural of the term it modifies, thereby including at least one of that term (for example, the dye (s) includes at least a dye). "Optional" or "optionally" means that the event or circumstance described subsequently may or may not occur, and that the description includes examples where the event occurs and cases where it does not. As used herein, "combination" is inclusive of combinations, mixtures, alloys, reaction products, and the like. All references are hereby incorporated by reference.
    [00090] The use of the terms "one" and "one" and "o / a" and similar referents in the context of the description of the invention (especially in the context of the following claims) should be interpreted as covering the singular and the plural, the unless it is otherwise indicated or clearly contradicted by the context. Furthermore, it should also be noted that the terms "first", "second" and others still here do not denote any order, quantity, or importance, but are used instead to distinguish one element from another. The "about" modifier used in relation to a quantity is inclusive of the indicated value and has the meaning dictated by the context (for example, it includes the degree of error associated with the measurement of the particular quantity).
    权利要求:
    Claims (20)
    [0001]
    1. Method for the production of polymer composite, characterized by the fact that it comprises: Mixing a thermoset polymer precursor, and 0.01 to 30% by weight of a derivatized nanoparticle, based on the total weight of the polymeric composite, the derivatized nanoparticle including functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactone, functionalized polymeric or oligomeric groups, or a combination comprising at least one of the foregoing functional groups the thermosetting polymer precursor, derivatized nanoparticles and functional groups are selected so that a variability in tensile strength, percentage elongation and average modulus to the polymer composite is less than the variability of these properties in which a non-derivatized nanoparticle is mixed with the thermorigid polymer precursor in place of the derivatized nanoparticle.
    [0002]
    2. Method, according to claim 1, characterized by the fact that the derivatized nanoparticle includes the functional group in an amount of 1 functional group per 5 carbon centers to 1 functional group per 100 carbon centers in the nanoparticle.
    [0003]
    3. Method according to claim 1, characterized by the fact that the derivatized nanoparticle is hydrophilic, hydrophobic, oleophilic, oleophobic, oxophilic, lipophilic, or a combination of these properties.
    [0004]
    4. Method, according to claim 1, characterized by the fact that the functional groups are alkyl, aryl, aralkyl, alkaryl, polymeric or functionalized oligomeric groups or a combination of these groups, and the functional groups are directly linked to the nanoparticle derived by a carbon-carbon bond without intervening heteroatoms, a carbon-oxygen bond or a carbon-nitrogen bond.
    [0005]
    5. Method, according to claim 1, characterized by the fact that the nanoparticle comprises a fullerene, a single or multiple wall nanotube, nanographite, nanographene, graphene fiber, nanodiamantes, polysilsesquioxanes, silica nanoparticles, nanoparticles clay, metal particles or combinations comprising at least one of the previous items.
    [0006]
    6. Method according to claim 5, characterized by the fact that the nanoparticle is a nanograph, a single-walled or multi-walled nanotube or a combination comprising at least one of the previous items.
    [0007]
    7. Method according to claim 5, characterized in that the nanographene preparation comprises exfoliation of nanographite by fluorination, acid intercalation, acid intercalation followed by heat shock treatment or a combination comprising at least one of the previous items.
    [0008]
    8. Method according to claim 1, characterized by the fact that the thermoset polymer precursor comprises fluorelastomers, perfluoroelastomers, hydrogenated butyl nitrile rubber, ethylene-propylene-diene monomer rubber (EPDM), silicones, epoxy , polyether etherketone, bismaleimide, polyethylene, polyvinyl alcohol, phenolic resins, polycarbonates, polyesters, polyurethanes, tetrafluoroethylene-propylene elastomeric copolymers, or a combination comprising at least one of the previous resins.
    [0009]
    9. Method according to claim 1, characterized by the fact that a polymer formed from the thermoset polymer precursor comprises a polyurethane, polyester attached to the urethra or a polyester attached to the urea.
    [0010]
    10. Method according to claim 1, characterized in that the thermoset polymer precursor and the derived nanoparticle comprise a dispersion in a solvent, and the solvent is an inorganic solvent comprising water, mineral acid or a combination comprising at least one of the previous items or an organic solvent comprising alcohol, ketone, oils, ethers, amides, sulfones, sulfoxides or a combination comprising at least one of the previous items.
    [0011]
    11. Method according to claim 10, characterized in that the dispersion is fluid under conditions of laminar or turbulent flow.
    [0012]
    12. Method according to claim 1, characterized by the fact that the Reynolds number for the dispersion is from 0.001 to 1,000.
    [0013]
    13. Method for the production of polymer composite, characterized by the fact that it comprises: derivatize a nanoparticle to include functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactone, groups polymerized or functionalized oligomers or a combination comprising at least one of the previous functional groups and mixing the derivatized nanoparticle with a thermoset polymer precursor, the thermoset polymer precursor, derivatized nanoparticles and functional groups being selected so that a variability in resistance to tensile strength, percent elongation and average modulus for the polymer composite is less than the variability of these properties in which a non-derivatized nanoparticle is mixed with the precursor thermoset polymer in place of the derivatized nanoparticle.
    [0014]
    14. Method according to claim 13, characterized in that the polymer formed from the thermoset polymer precursor is a polyurethane, urethane-bound polyester or urea-bound polyester.
    [0015]
    15. Method according to claim 14, characterized by the fact that polyurethane, urethane-bound polyester or urea-bound polyester are formed by combining a compound with at least two isocyanate groups and a polyol, diamine or a combination comprising at least one of the previous items.
    [0016]
    16. Method according to claim 15, characterized in that the compound with at least two isocyanate groups and the polyol and / or diamine are mixed simultaneously.
    [0017]
    17. Method according to claim 15, characterized by the fact that the compound having at least two isocyanate groups and the polyol, diamine or combination thereof is added sequentially.
    [0018]
    18. Method according to claim 13, characterized by the fact that it contains 0.05 to 20% by weight of derivatized nanoparticles, based on the total weight of the polymer composite.
    [0019]
    19. Method according to claim 13, characterized in that the polymer composite is a dispersion in a solvent.
    [0020]
    20. Method for the production of polyurethane nanocomposite, characterized by the fact that it comprises: derivatize a nanoparticle to include functional groups comprising carboxy, epoxy, ether, ketone, amine, hydroxy, alkoxy, alkyl, aryl, aralkyl, alkaryl, lactone, groups polymerized or functionalized oligomers or a combination comprising at least one of the above functional groups, and mixing 0.05 to 20% by weight of derivatized nanoparticles, a precursor to a polyurethane, urea-bound polyester or urea-bound polyester, comprising: a compound with at least two isocyanate groups, and a polyol, a diamine or a combination thereof, the amount of derivatized nanoparticles being based on the total weight of the polyurethane nanocomposite, and the precursor, the derivatized nanoparticle and the groups Functional components are selected so that a variability in tensile strength, percentage elongation and average modulus for the nanocomposites polyurethane content is less than the variability of these properties, and a non-derivatized nanoparticle is mixed with the precursor in place of the derivatized nanoparticles.
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    同族专利:
    公开号 | 公开日
    US20120065309A1|2012-03-15|
    CN103108908A|2013-05-15|
    AU2011299118B2|2013-09-26|
    CA2808130A1|2012-03-15|
    US8318838B2|2012-11-27|
    BR112013005666A8|2016-10-11|
    AU2011299118A1|2013-02-21|
    CN103108908B|2014-07-23|
    CA2808130C|2016-02-16|
    WO2012033995A3|2012-06-14|
    WO2012033995A2|2012-03-15|
    BR112013005666A2|2016-05-03|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2019-12-17| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-06-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-09-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/09/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/878,507|US8318838B2|2010-09-09|2010-09-09|Method of forming polymer nanocomposite|
    US12/878,507|2010-09-09|
    PCT/US2011/050956|WO2012033995A2|2010-09-09|2011-09-09|Method of forming polymer nanocomposite|
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