CROSS-LINKED AND RECYCLABLE ELECTROCONDUCTIVE CARBONACEOUS NANOCOMPOUNDS AND POLYMERS CAPABLE OF DISPERSING AND STABILISING THEM, METHOD, DERIVED MATERIALS AND USES

Abstract

The present invention relates to cross-linked and recyclable nanocompounds obtained by in situ terminal treatment of raw carbonaceous materials, including charcoal, tar, activated carbon, pyrolytic carbon, coke, graphite or others having conductive structures, including graphite, graphene, different carbon nanotubes, fullerenes or a combination thereof or their derivatives, and a polymer capable of dispersing and reversibly stabilising said components, having viscous or fluid behaviour below 200° C., and may have pendant groups acting as diene or dienophile, including furan-functionalised aliphatic polyketones, furan-functionalised polyesters, ethylene rubber with propylene functionalised with furan groups or a combination thereof. Derived materials, method of obtainment and their uses as a thermostable, thermoreversible, thermoadhesive, thermoconductive, electroconductive, self-repairing additive or matrix capable of converting electricity into heat or a combination thereof and in self-assembling or self-repairing, thermoconductive, electroconductive materials capable of converting electricity into heat or a combination thereof.

Claims

1-93. (canceled)

94. Cross-linked and recyclable nanocomposites comprising electricity-conducting carbonaceous materials and a polymer capable of dispersing and stabilizing such carbonaceous materials, where said electricity-conducting carbonaceous materials are selected from graphite, graphene, charcoal, pitch, activated carbon, pyrolytic carbon, coke, combustion residues of organic material, or a combination thereof or their derivatives, and where said polymer is a polytone derivatized with primary amines, alcohols or mercaptans, where said primary amines, alcohols, or mercaptans contain hanging groups acting as diene or dienophile, or a combination thereof, selected from cyclopentadiene, dicyclopentadiene, furan, butadiene, anthracene, tetracene, pentacene, maleimide, maleic anhydride, maleic imida, benzoquinone, alkyn, alkene, phthalic, or a combination thereof, where said derivatized polytone has a carbon chain length greater than 50 carbons, and where said derivatized polytone has a glass transition temperature or melting temperature or both, below 200° C.

95. The nanocomposites of claim 94, wherein the diene or dienophile groups contained in said primary amines, alcohols, or mercaptans are selected from furan.

96. The nanocomposites of claim 95, wherein said primary amine substituted with groups comprising diene or dienophile is furfurilamine.

97. The nanocomposites of claim 94, wherein said polytone derivatized with primary amines, alcohols or mercaptans has additional hanging groups selected from saturated and unsaturated hydrocarbon chains, alcohols, amines, esters, ethers, polyethers, mercaptans, carboxylic acids, sulfates, sulfonates, sulfones, phosphates or phosphonates.

98. The nanocomposites of claim 97, wherein the hanging groups have spacer groups of short carbon chain or long carbon chain selected from polystones, polyesters, polyethers, polyamines, polyolefins, or their functionalized derivatives.

99. Cross-linked and recyclable nanocomposites according to claim 94, wherein said electricity-conducting carbonaceous materials being selected from graphite of macrometric, micrometric, and nanometric dimensions.

100. Cross-linked and recyclable nanocomposites in accordance with claim 94, wherein they also comprise a cross-linker of reversible joints between said carbonaceous material and said polymer, as well as polymer with polymer and carbonaceous material with carbonaceous material.

101. Cross-linked and recyclable nanocomposites according to claim 100, wherein said a reversible junction cross-linker is bis-maleimide.

102. Cross-linked and recyclable nanocomposites in accordance with claim 94, wherein they comprise additional organic and inorganic components, of macrometric, micrometric or nanometric size, selected from wood and paper derivatives, cellulose fibers, polymers, silica particles, diatomaceous earth, minerals, metal oxides, metal salts, metal particles, metals, or asphalt bitumen.

103. Cross-linked and recyclable nanocomposites according to claim 102, wherein said wood and paper derivatives are selected from chips, sawdust, cellulose pulp or cellulose; such metal oxides are selected from copper oxide, titanium oxide and zinc oxide, said metal salts are selected from lithium salts, copper salts, and said metals are selected from copper, titanium, zinc, aluminum, silver and gold.

104. Cross-linked and recyclable nanocomposites according to claim 94, wherein they are useful in the manufacture of thermoconductive materials, electroconductors, heat electricity converters, filler compositions, self-repairing materials with electricity, self-repairing materials with heat, self-assembling materials with electricity, self-assembling materials with heat, additives, binders, when mixed with various materials chosen from: carbonaceous materials including wood and paper derivatives; polymers; silica particles; diatomaceous earth; minerals; metal oxides; metal particles; metals or asphalt bitumen.

105. A method of preparation of the nanocomposites of claim 94, comprising: (a) functionalising a polytone by means of a Paal-Knorr reaction with primary amines, alcohols or mercaptans having hanging groups acting as diene or dienophile, where such primary amines, alcohols or mercaptans are in a molar proportion to the diketone groups of said polytone in the range of 1 and 100%, and where said Paal-Knorr reaction takes place at temperatures between 0° and 200° C.; (b) mixing the functionalised polyacetone obtained in step (a) with a selected carbonaceous material of graphite, graphene, charcoal, pitch, activated carbon, pyrolytic carbon, coke, combustion residues of organic material, or a combination thereof or their derivatives, where such mixing is carried out at the glass transition temperature or at the melting temperature of the functionalised polymer obtained in step (a) until an increase in the viscosity of the mixture is achieved referring to a good dispersion and homogeneity followed by the cooling of the mixture to room temperature, and where the proportion of said polymer functionalized with hanging groups that act as diene or functionalized dienophile and carbonaceous materials is in the range 10%:90%-99.9%:0.1%; and (c) cooling the mixture where stages a) and/or b) are performed in the absence or presence of solvent.

106. The method of claim 105, wherein it includes subjecting the mixture resulting from step c) to successive cycles of heating and cooling, until reaching a constant viscosity of the final product.

107. The method of claim 105, wherein, subsequently, the nanocomposite is subjected to grinding, compression molding, injection, extrusion, electrospinning, lyophilization, expansion, using or not supercritical solvents or fluids, or a combination of both, to give it a selected form of powder, fiber, prism, monolith, sheet, sponge or aerogel.

108. The method of claim 105, wherein said diene or dienophilic groups contained in said primary amines, alcohols, or mercaptans are selected from cyclopentadiene, dicyclopentadiene, furan, butadiene, anthracene, tetracene, pentacene, maleimide, maleic anhydride, maleic imida, benzoquinone, alkynone, alkene, phthalic, or a combination thereof.

109. The method of claim 108, wherein said primary amines with hanging groups comprising diene or dienophile groups are selected from primary amines comprising furan.

110. The method of claim 109, wherein said primary amine comprising furan is furfurylamine.

111. The method of claim 105, wherein when steps a) and/or b) are conducted in the presence of solvent, said solvent is selected from water, tetrahydrofuran (THF), acetonitrile, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), 2 propanol, 1 propanol, ethanol, toluene, benzene, chlorobenzene, 1,2-dichlorobenzene chloroform, dichloromethane, saturated or unsaturated alicyclic alicyclic hydrocarbon, an aromatic hydrocarbon, an alcohol comprising at least 3 carbon atoms, a glycol, a halogenated hydrocarbon, a ketone, an ester, an ether, a glycol ether or a mixture of two or more thereof.

112. The method of claim 111, wherein said solvent is THF, 1-propanol, chloroform, dichloromethane, or dimethylformamide (DMF).

113. The method of claim 105, wherein simultaneously or after stage a), additional derivatizations of such polytones are performed with primary amines, alcohols or mercaptans containing selected organic groups of saturated and unsaturated carbon chains, alcohols, amines, esters, ethers, polyethers, mercaptans, carboxylic acids, sulfates, sulfonates, sulphones, phosphates or phosphonates.

114. The method of claim 105, wherein in stage b), such electricity-conducting carbonaceous materials are selected from graphite of macrometric, micrometric, and nanometric dimensions.

115. The method of claim 105, wherein in stage a) said proportion of polytone and said primary amine with hanging groups comprising diene or dienophile groups comprising furan, is in the range 80%:20%-99.9%:0.1%.

116. The method of preparation of materials according to claim 105, wherein it additionally includes the stage: (d) adding additives in one or both of stages (a), (b), or after (c), where said additives are selected from bismaleimide, maleic anhydride, maleic amide, benzoquinone, alkyn, alkene, or organic and inorganic materials of macrometric, micrometric or nanometric size, selected from wood and paper derivatives, cellulose fibres, polymers, silica particles; diatomaceous earth, minerals, metal oxides, metal salts, metal particles, metals, or asphalt bitumen, where said mixing is carried out at temperatures above the glass transition temperature or above the melting temperature of the functionalized polymer obtained in stage a).

117. The method of claim 116, wherein said derivatives of wood and paper are selected from shavings, sawdust, cellulose pulp or cellulose; said metal oxides are selected from copper oxide, titanium oxide and zinc oxide, said metal salts are selected from lithium salts, and copper salts, and said metals are selected from copper, titanium, zinc, aluminum, silver and gold.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0029] FIG. 1. Schematic representation of PK functionalized with furan (PK-Fu) or benzyl (PK-Bea) groups through the Paal-Knorr reaction.

[0030] FIG. 2. Functionalization of MWCNT with (A) PK-Fu (diene) and (B) bis-maleimide (dienophile) by Diels-Alder reaction.

[0031] FIG. 3. X-ray photoemission spectrum of the central level regions of Cls, Nls and Oís of MWCNTs functionalized with PK-Fu. Data and fit lines are displayed.

[0032] FIGS. 4A-4C. Photograph of the conductive polyketone nanocomposite grafted with furanyl groups, cross-linked with multi-walled carbon nanotubes and bismaleimide added as a connected additive to the electrical circuit 4A and its thermal images before (FIG. 4B) and during the application of a voltage of 35 V (4C).

[0033] FIG. 5. Microscopic images of the conductive polyketone nanocomposite grafted with furanyl groups, crosslinked with multiwalled carbon nanotubes and bismaleimide added as an additive. Area examined undamaged (FIG. 5A), damaged (FIG. 5B) and self-repaired with electricity (FIG. 5C).

[0034] FIG. 6. Shows the self-repair of the nanocomposite with temperature using the Diels-Alder sequence. (1) torn, (2) self-healing front face (3) self-healing back face.

[0035] FIG. 7: Correlograms in DLS experiments of a suspension of the polymer with graphite microparticles (a) graphite particles of micrometer size and in red the decrease in the size of the graphite particles to nanometric size after the exfoliation treatment with modified polyketone.

[0036] FIG. 8. Photograph of derivatized polyketone/graphene-like carbonaceous nanostructures after compression molding and connected to electricity generating 150° C.

[0037] FIG. 9. Photograph of two derivatized polyketone monolithic nanocomposites/graphene-like carbonaceous nanostructures after self-assembling in an oven at 150° C.

[0038] FIGS. 10A and 10B: Imaging of polymer with nano-sized graphite particles before compression molding with sawdust (FIG. 10A) and after compression molding with sawdust (FIG. 10B).

[0039] FIG. 11. Photograph of derivatized polyketone/graphene-like carbonaceous nanostructures after compression molding and connected to electricity generating 150° C. and showing self-repair of a surface crack.

[0040] FIGS. 12A and 12B. Viscoelastic behavior of asphalt bitumen (FIG. 12A) and derivatized polyketone/graphene-like nanostructures after mixing with asphalt bitumen and compression molding showing rheological properties superior to bitumen alone (FIG. 12B).

[0041] FIG. 13. DCS thermal cycling of the polyketone nanocomposite derivatized with furanyl groups (PK-Fu) and multi-walled carbon nanotubes (MWCNT).

[0042] FIG. 14. DSC thermal cycling of the polyketone nanocomposite derivatized with furanyl groups (PK-Fu) and multi-walled carbon nanotubes (MWCNT) reinforced with the additive bismaleimide

[0043] (B-Ma).

[0044] FIG. 15. DMTA of a polyketone nanocomposite derivatized with furanyl groups (PK-Fu) and multi-walled carbon nanotubes (MWCNT) reinforced with the additive bismaleimide (B-Ma) and its annealing by resistive heating for 24 h with 35 V.

[0045] FIG. 16. Variation of the absolute impedance of the polyketone nanocomposite derivatized with furanyl groups (PK-Fu) and multi-walled carbon nanotubes (MWCNT) reinforced with the additive bismaleimide (B-Ma) and its annealing by resistive heating for 24 h with 35 V.

[0046] FIG. 17. SEM micrographs of the polyketone nanocomposite derivatized with furanyl groups (PK-Fu) and multi-walled carbon nanotubes (MWCNT) reinforced with the bismaleimide additive (B-Ma) after molding (A, C) and after annealed by resistive heating (B, D).

DETAILED DESCRIPTION OF THE INVENTION

[0047] The present invention refers to cross-linked and recyclable nanocomposites that can be used as additive or matrix for the manufacture of materials, and that provide properties of thermostability, thermoreversibility, thermoadhesiveness, thermoconductivity, electroconductivity, self-repair, self-assembly, conversion of electricity into heat, or a combination of them. Said nanocomposites can be obtained by an in situ method by thermal treatment, from raw carbonaceous materials (Pure and Applied Optics 40 (2) 149-159 (2007)), including char, pitch, activated carbon, pyrolytic carbon, coke, graphite, organic material combustion residues, or selected from other carbonaceous materials comprising conductive structures, including graphite, graphene, carbon nanotubes including multi-walled carbon nanotubes and single-walled carbon nanotubes, fullerenes, or a combination of the themselves or their derivatives, and a polymer capable of reversibly dispersing and stabilizing said components, where said polymer has a viscous or fluid behavior below 200° C., where said polymer is selected from a derivatized polymer with pendant groups that act as diene or dienophilic, preferably said derivatized polymer with pendant groups acting as diene or dienophilic is selected from furan functionalized aliphatic polyketones, furan functionalized polyesters, ethylene gum with propylene functionalized with furan groups or a combination thereof. The invention also relates to materials derived from these nanocomposites that import their unique inherent properties to give them properties of thermostability, thermoreversibility, thermosetting, thermoconductivity, electroconductivity, self-repair, self-assembly, conversion of electricity into heat, or a combination thereof. The invention also relates to a method of obtaining said nanocomposites, and their use as an additive or matrix thermosetting, thermoreversible, thermoadhesive, thermoconductive, electroconductive, self-repairing, converting electricity into heat, or a combination thereof.

[0048] In order to obtain viscosity and fluidity properties below 200° C., said aliphatic polyketone is selected from low molecular weight polyketones, preferably with a carbon chain length greater than 50 carbons, preferably greater than 100 carbons, more preferably the carbon chain length is in the range of 100-500 carbons, even more preferably 120-200 carbons. Said aliphatic polyketone can also be selected from high molecular weight polyketones, preferably with molecular weights greater than 10,000 daltons, preferably greater than 50,000 daltons, even more preferably greater than 100,000 daltons, and even more preferably in the range of 50-500 thousand daltons, and even more preferably it is in the range between 100 to 200 thousand daltons. In these cases, the goal of viscosity and fluidity below 200° C. can be achieved by derivatization reactions with organic side groups, such as saturated and unsaturated alkyl groups, alcohols, amines, esters, ethers and polyethers, mercaptans, etc.

[0049] The nanocomposites of the present invention are cross-linked, thermoset and recyclable, they are conductive, thermally reversible, and present possibilities of thermomechanical reprocessing and stable electrical response; in addition, they behave like a thermoplastic when heated or pressed. Preferably they comprise viscous and fluid polymers below 200° C., derivatized with diene and dienophilic groups that have characteristics of formation of reversible, easily processable thermoset polymers, including polyketones derivatized with pendant chemical groups that act as diene or dienophiles, capable of producing Reversible Diels-Alder reactions. Results obtained demonstrate the successful chemical modification of polyketone with a variety of functional chemical groups. In particular, the derivatization of polyketones with furanyl groups leads to polymers with the desired characteristics to link reversibly electrically conductive carbonaceous structures (FIG. 1).

[0050] These functional polymers, being viscous and fluid below 200° C., show reversible properties, softening temperature, melting temperature and degradation temperature that provide a direct way to design adjustable thermosetting and self-healing nanocomposites. This allows the systematic formation of polymer molecular structures that optimizes the balance between the glass transition temperature and the melting temperature of the polymers based on the temperature necessary for crosslinking and subsequent opening of the thermosetting polymer during self-healing procedures with thermal energy. conventional or electric Joule effect.

[0051] From an applicative point of view, these functional polymers exhibit reversible properties, softening temperature, melting temperature, and degradation temperature that provide a direct way to design adjustable self-healing and thermosetting nanocomposites. This allows for systematically forming polymer molecular structures that optimize the balance between the glass transition temperature and the melting temperature of the polymers based on the temperature necessary for crosslinking and subsequent opening of the thermosetting polymer during self-healing procedures with conventional thermal energy. or electric Joule effect. Therefore, the intrinsic activation of self-healing, in particular the disconnection/reconnection of the Diels-Alder interactions makes it possible to systematically establish which molecular structure of the polymer with active Diels-Alder groups and the inherent properties with conductive carbonaceous structures and the fraction of volume that optimize the balance between the glass transition temperature and the melting temperature of the polymers and the heat energy necessary to cross-link and subsequently open the thermosetting nanocomposites during self-repair procedures. The latter is crucial to design fully self-healing thermoset nanocomposites taking into account the kinetics and energy levels for the crosslinking and opening reactions of the structurally damaged composite material, thus avoiding the need for higher energy levels for crosslinking and opening of the composite material that can degrade the material.

[0052] In a specific embodiment of the invention, mixing 5% by weight of carbon nanotubes with a polyketone functionalized with furanyl groups produces a conductive nanocomposite that exhibits thermal and electrically conductive properties (FIG. 2). X-ray spectroscopy analysis indicates that carbon nanotubes, due to their diene/dienophilic character, interact covalently with the matrix through the Diels-Alder reaction, leading to effective interfacial adhesion between the components (FIG. 3). The nanocomposite could be converted into a monolithic material with thermal and electrically conductive properties by compression and heating molding (FIG. 4A, for example). Additionally, the mechanical properties of monolithic materials could be strengthened by crosslinking the nanocomposite obtained by the Diels-Alder reaction with bis-maleimide added as an additive during molding processing. Thus, the softening point (tan (d) in dynamic mechanical analysis measurements) reaches up to 155° C., producing a material with good mechanical characteristics. After grinding the composite material, compression molding (150° C./4 MPa (40 bar)) activates the retro-Diels-Alder process that disassembles the web, allowing it to be reshaped as a thermoplastic. A subsequent process of annealing using resistive heating demonstrates the possibility of reconnecting the uncoupled Diels-Alder bonds, thus providing the nanocomposite with the properties of recyclability, reusability, and reprocessing in different ways, as well as the self-repair of cracks using electricity (FIG. 5).

[0053] On the other hand, as a test, an electrically activated thermoconductive monolithic material was manufactured from the functional nanocomposite obtained both using solvents and by mechanical mixing without solvents, drying, grinding, and subsequent compression molding. Once the material was connected to an electrical circuit, its usability to irradiate heat by resistive heating could be verified (FIGS. 4B and 4C).

[0054] Two thermoconductive monolithic materials were also prepared from the functional nanocomposite obtained both using solvents and by mechanical mixing without solvents, drying, grinding, and subsequent compression molding. Once both materials were in contact and by connecting each one to the ends of an electrical circuit, it was found that the two composite materials could be self-assembled to generate a single monolithic structure.

[0055] Two thermoconductive monolithic materials were also prepared from the functional nanocomposite obtained both using solvents and by mechanical mixing without solvents, drying, grinding, and subsequent compression molding. Once both materials were put in contact and heated in the oven to 150° C., it was found that the two composite materials could be reprocessed, self-assembled and recycled to generate a single monolithic structure (FIG. 6).

[0056] In another specific embodiment of the invention, when heating a derivatized polymer with furanyl groups mixed with graphite microparticles (20 μm), the exfoliation of graphite in graphene-like nanostructures (200 nm) occurs (FIG. 7), and, after an after-cooling, a nanocomposite is produced that shows very good dispersion and stabilization of graphene-type nanostructures. This is inferred with the naked eye by the lack of precipitation of the graphite powder and, analytically, by verifying the presence of nano-sized structures in the mixture by the dynamic light scattering (DLS) technique (FIG. 7). The resulting material exhibited good electron conducting properties. A stable and homogeneous powder mixture of the resulting nanocomposite was subsequently obtained, suggesting that the polymeric matrix has a strong exfoliating effect on the graphite filler, an outstanding characteristic that allows graphene nanostructures to be exfoliated in situ from bulk graphite and its subsequent use. in the manufacture of functional materials.

[0057] Additionally, an electrically activated thermoconductive monolithic material was obtained from the functional nanocomposite obtained both using solvents and by mechanical mixing without solvents, drying, grinding, and subsequent compression molding. Once the material was connected to an electrical circuit, its usability to irradiate heat by resistive heating could be verified (FIG. 8).

[0058] Two thermoconductive monolithic materials were also prepared from the functional nanocomposite obtained both using solvents and by mechanical mixing without solvents, drying, grinding, and subsequent compression molding. Once both materials were in contact and by connecting each one to the ends of an electrical circuit, it was found that the two composite materials could be self-assembled to generate a single monolithic structure.

[0059] Two thermoconductive monolithic materials were also prepared from the functional nanocomposite obtained both using solvents and by mechanical mixing without solvents, drying, grinding, and subsequent compression molding. Once both materials were brought into contact and heated in the oven to 150° C., it was found that the two composite materials could be self-assembled to generate a single monolithic structure (FIG. 9).

[0060] Likewise, a monolithic material was obtained by mixing the functional nanocomposite obtained and sawdust particles, both using solvents, as well as mechanical mixing without solvents and powder mixing, drying, grinding, and subsequent compression molding. The resulting material is a wood-filled composite that conducts electricity (FIG. 10A and 10B)

[0061] Additionally, an electrically self-repairing monolithic material was prepared from the functional nanocomposite obtained, both using solvents and by mechanical mixing without solvents, drying, grinding, and subsequent compression molding. A mechanical crack was made in the material and, once it is connected to an electrical circuit, it was found that the material heats up, softens locally and self-repairs the mechanical damage (FIG. 11).

[0062] Likewise, an additive was prepared from the functional nanocomposite obtained, which, mixed with asphalt bitumen, both using solvents and mechanical mixing without solvents, drying, grinding, and subsequent compression molding, was characterized by rheology, determining an increase between 6 to 8 times the rheological properties of bitumen asphalt (FIG. 12).

[0063] In all these cases, because the covalent interaction between the derivatized polymers with diene or dienophilic groups, preferably modified polyketone, and the electrically conductive carbonaceous nanostructures is reversible, the resulting system could be subjected to such a temperature (150° C.) that allows the separation of the components, either by conventional caloric stimulation or resistive heating by electricity. In an event of structural damage, the material could be self-healing or two composite materials of the same or different material could be self-assembled to generate a single structure. For the same reason, the nanocomposites of the present invention offer recycling properties by conventional heat stimulation or electrical by resistive heating.

[0064] Regarding the self-repair mechanism, it would operate in the following way, without adhering to any theory: electrically induced self-repair occurs through the generation of nanoscopic heat when an electric current passes through the nanostructured conductive network of conductive carbonaceous materials. This resistive heating activates the intrinsic self-healing ability of the thermally self-healing polymer matrix to repair damage in local areas. The chemical pathway used for thermal self-repair is Diels-Alder reversible cycloaddition. This allows for bond breaking, molecular movements, and reconnection of matrix molecules and carbonaceous structures through retro-Diels-Alder and Diels-Alder reactions, respectively, and therefore regeneration of three-dimensional network structures.

[0065] In a specific embodiment of the invention, the activation of resistive heating using electricity in the presence of macroscale damage (i.e. cuts), generates local changes in electrical resistivity in the crack and leading to a local increase in temperature, within of the temperature range of the retro-Diels-Alder reaction. Said temperature generates the opening of the cross-linked network of the polimeric matrix to in turn generate enough mobility in the polymeric chains to close and seal the cut through the Diels-Alder reaction when cooling.

[0066] In a specific embodiment of the invention, the method of preparing the nanocomposites comprises the following steps:

[0067] a) functionalizing a polymer with pendant groups that act as diene or dienophilic, where preferably said polymer is selected from an aliphatic polyketone, and said functionalization carried out carried out by means of a Paal-Knorr reaction between said aliphatic polyketone and primary amines containing said diene or dienophilic groups, preferably, but not limited to, furfurylamine, being the molar ratio between the dicarbonyl groups of said aliphatic polyketone, where said primary amine allows conversion percentages between 1 and 100%, preferably in the range of 20-90%, more preferably in the range of 40-85%, more preferably in the range of 60-80%, the molar proportion of groups being then Aliphatic polyketone diketone and furfurylamine in the range of 1 and 100%, preferably in the range of 20-90%, more preferably in the range of 40-85%, more preferably in the range of 60-80%. The reaction is carried out at temperatures between 50 and 200° C., preferably at 100° C. in the absence of solvent, or alternatively using at least one solvent, which can be selected from saturated or unsaturated aliphatic or alicyclic hydrocarbon, a hydrocarbon aromatic, an alcohol preferably comprising at least 3 carbon atoms, a glycol, a halogenated hydrocarbon, a ketone, an ester, an ether or a glycol ether, or a mixture of two or more thereof, preferably selected from tetrahydrofuran (THF), acetonitrile, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), 2 propanol, 1 propanol, toluene, benzene, chlorobenzene 1,2-dichlorobenzene, still preferably 1 propanol;

[0068] b) optionally, additional derivatizations of the polyketones with organic side groups, including saturated and unsaturated alkyl groups, alcohols, amines, esters, ethers and polyethers, mercaptans, can be carried out under the same methodology of step a), in order to modulate the temperatures glass transition, melting temperature or both below 200° C. in order to give the polymers the desired viscosity and fluidity.

[0069] c) mixing the functionalized polymer obtained in step a) with a carbonaceous material selected from raw carbonaceous materials comprising electrically conductive carbonaceous materials including carbon, pitch, activated carbon, pyrolytic carbon, coke, graphite, combustion residues of organic material, or Electrically conductive carbonaceous materials selected from graphite, graphene, and carbon nanotubes, including single or multiple walled carbon nanotubes, fullerenes, or a combination thereof or their derivatives, where said mixing is carried out at temperatures above the melting temperature of the polymer until the establishment of the retro-Diels Alder reaction preferably, including in the temperature range between 20 and 200° C., preferably between 40 and 120° C., in the absence of solvent, or alternatively in the presence of a solvent selected from water or organic solvents such as saturated or unsaturated aliphatic or alicyclic hydrocarbon, an aromatic hydrocarbon, an alcohol preferably comprising at least 3 carbon atoms, a glycol, a halogenated hydrocarbon, a ketone, an ester, an ether or a glycol ether, or a mixture of two or more thereof, preferably selected from tetrahydrofuran (THF), acetonitrile, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), 2 propanol, 1 propanol, toluene, benzene, chlorobenzene 1,2-dichlorobenzene, where the proportion of derivatized polymer with pendant groups acting as furan functionalized diene or dienophile, where the proportion by weight of furan and carbonaceous materials is in the range 10%: 90% - 99.9%: 0.1%, preferably 80%: 20% -99.9%: 0.1%, and the volume of solvent in the range of 90% -10% in ml, preferably in the range of 50% -10% in ml;

[0070] d) optionally, over the hot reaction mixture, additives, including crosslinkers comprising one of bis-maleimide, maleic anhydride, maleic imide, benzoquinone, alkyne, alkene, cellulose fibres, inorganic particles, metal salts, salts of lithium, copper salts, metal oxides including titanium oxides, zinc oxide, copper oxide, metal nanoparticles including gold and silver nanoparticles, metals, polymeric materials to manufacture advanced materials with various properties;

[0071] e) optionally separating the non-conductive residues from the crude carbonaceous materials by precipitation, centrifugation, filtration, or other conventional methods;

[0072] f) cooling the mixture, optionally grinding the nanocomposite, and storing, and optionally using it to shape it by techniques including compression molding, injection, supercritical fluid treatment, where such shapes include powder, prism, monolith, sheet, sponge, airgel.

[0073] Examples illustrating the present invention, without limiting it, are provided below, the technical embodiments being equivalent to these examples, contained within the spirit and scope of the invention. The following examples then seek to allow the understanding of the invention, without restricting its scope, and in particular, to comprise a preferred embodiment for obtaining polyketone derivatized with furanyl groups, obtaining nanocomposites of polyketone derivatized with furanyl groups and carbon nanotubes, Obtaining derivatized polyketone nanocomposites with furanyl groups, carbon nanotubes and the bismaleimide additive, obtaining nanocomposites of polyketone derivatized with furanyl groups and exfoliated graphite in situ in graphite nanostructures, and their advantageous properties, and possible applications with different additives and their forms.

Examples

Example 1: Functionalization of polyketone with furan groups

[0074] The reaction between polyketone (PK) and furfurylamine (Fu) was carried out in bulk by the Paal-Knorr reaction. The polyketone functionalized with furan groups (PK-Fu) (FIG. 1) was made without solvent according to the molar ratio between the 1,4-di-carbonyl groups of polyketone and furfurylamine. In particular, the synthesis of PK-Fu was carried out in a 250 ml sealed round bottom glass reactor with a reflux condenser, a U type anchor impeller and an oil bath for heating. After preheating 10 g of PK to a liquid state at 100° C., furfurylamine was added to the reactor. The stirring speed was set at 600 rpm and the reaction time was set at 4 h. The resulting polymers were washed 3 times with Milli-Q water to remove any unreacted furfurylamine. Subsequently, the remaining water was removed under vacuum in a lyophilizer for 72 h.

[0075] The summary of the experimental results is shown in Table 1

TABLE-US-00001 TABLE 1 Experimental results of PK modified with furfurylamine (PK-Fu). Run C.sub.co(%) .sup.a T.sub.g(° C.) .sup.b PDI .sup.c PK-Fu 74 31 2.3 .sup.a carbonyl conversion; .sup.b glass transition temperature, .sup.c polydispersity index.

[0076] The characterization of PK-Fu by means of.sup.1H NMR spectroscopy of the polymer indicates the presence of protons attributed to the CH.sub.2 groups between the pyrrole and furan groups at 4.9 ppm, the one related to the pyrrole group at 5.8 ppm and the Proton signals from the furan residues at 5.9, 6.2 and 7.3 ppm. FT-IR spectroscopy of the same sample shown indicates the presence of bands of CH bonds related to heterocyclic groups around 3150-3115 cm.sup.−1 —(pyrrole and furan groups), the band of C=O bonds of groups carbonyl at 1707 cm.sup.−1, the C=C bond band of heterocyclic groups at 1507 cm.sup.−1, the C—N bond bands of the pyrrole group are observed at 1345 cm.sup.−1, the C—O—C bond bands of the furan group are observed at 1073 cm.sup.−1 - and, finally, the C—H bond band out of plane of the furan ring at 735 cm.sup.−1.

[0077] The glass transition temperature of PK-Fu (Tg) was measured by DSC (Table 1) and reaches a value of 31° C. The polydispersity of PK-Fu was determined by GPC (Table 1) showing characteristics of secondary standard.

[0078] The carbonyl conversion (Cco) indicates the percentages of furan groups grafted on the polyketone (Table 1).

Example 2: Nanocomposite Formation Between Carbon Nanotubes (MWCNT) and Aliphatic Polyketone Derivatized with Furan Groups

[0079] In a round bottom flask 0.95 g of PK-Fu was weighed which was dissolved in 5 ml of NMP (N-methyl-2-pyrrolidone) and added to 0.05 g of MWCNT. The reaction was stirred vigorously at 50° C. for 24 h using an oil bath equipped with a temperature controller. The reaction mixture was repeatedly washed with THF and filtered to recover the added MWCNTs with PK-Fu (see recovered product in Table 2). The remaining solvent was removed in vacuo at 50° C. for 48 h.

TABLE-US-00002 TABLE 2 Experimental results for the functionalization of MWCNT with PK-Fu. Sample N Content (%) Aggregate (%).sup.a MWCNT/PK-Fu 2.45 34 .sup.aThe amount of PK-Fu (%) on the surface of the MWCNT is estimated by elemental analysis according to the nitrogen content (N)).

[0080] FIG. 2 schematically shows the reaction between MWCNT and PK-Fu. An XPS analysis of PK-Fu functionalized MWCNTs clearly confirmed the effectiveness of the DA graft mechanism (FIG. 3). In the carbon 1 spectra, the main peak can be identified at 284.5 eV, accompanied by the shaking characteristic at approximately 6.0 eV of highest binding energy characteristic of the conjugated systems π-π, which would fit perfectly with C Sp.sup.2. On the other hand, the C1s spectrum of the pure polymer shows a broad characteristic that peaked at 286.0 eV and that results from three components, that is, C— C Sp.sup.2, —CH.sub.2—CH.sub.3 sp.sup.a and CH.sub.2—C—CH.sub.3. The spectrum for pure PK-Fu also shows 01 components attributed to 0=C at 532.4 eV and O-C at 533.8 eV, as well as a peak of N1s at 401.5 eV. For the nanocomposite from PK-Fu to MWCNTs, the presence of the polymer would be evident from the intensities of N1 and 01, but it could also be clearly confirmed in the carbon spectra. In the 01s spectrum, the results of the OC component shifted by 1 eV to a higher binding energy, which would clearly point to a charge redistribution resulting from the fixation of furan on the MWCNT surface, from which it would be possible to conclude - from the C1s spectrum, that the functionalization of the side wall of MWCNTs with PK-Fu would be carried out through the C—C bond.

[0081] Raman spectroscopy analyses of pristine MWCNTs and the nanocomposite show the G band, which testifies to the graphical crystalline arrangement (1580 cm.sup.−1), the defect-related D band (1345 cm.sup.−1) and the overtone of the D band, G′ band, are indicative of multi-walled structures (2684 cm.sup.−1). The band centered at 2995 cm.sup.−1 (CH vibration of alkanes) is only detected in the presence of the polymer. The intensity ratio between the D and G bands decreases from 1.49 for pristine MWNTs to 1.29 for PK-Fu functionalized MWCNTs. Then, after the cycloaddition step, the subsequent rehybridization would restore the Sp.sup.2 state, recovering the aromaticity of the system in the defective region of the MWCNTs. The highly defective graphene layers can also be followed by key analysis of the intensity relationship between the G ‘and D bands, increasing from 0.17 for pristine MWCNTs to 0.27 for the less entangled PK-Fu functionalized MWCNTs. In summary, although PK-Fu modifies the graphical surface of MWCNTs, its presence would enhance the long-range graphical order of pristine MWCNTs.

[0082] The DSC analysis of the PK-Fu nanocomposite (FIG. 13) shows two endothermic transitions: around 75-80° C., associated with the glass transition of the material, and the second from 120 to 170° C., centred at 160° C. and associated to the retro-DA reaction. The energy required for the retro-DA process reaches 11.6 J/g, a value that perfectly correlates with the energy associated with the retro-DA reaction for conventional thermally reversible crosslinked furan/maleimide systems. In this way, the MWCNT/PK-Fu represents a consistent example of a reversible graft between an electrically conductive graphite material and a polymer matrix.

Example 3: Reinforcement of the Nanocomposite with Bis-Maleimide Crosslinker

[0083] The thermosetting nanocomposite with the bis-maleimide crosslinker was prepared by mixing the product from Example 2 and equimolar amounts of PK-Fu and bis-maleimide using THF as solvent (10% by weight) in a 150 ml round bottom flask. equipped with a magnetic stirrer. The reaction mixture was heated at 50° C. for 24 h to form the cross-linked network under reflux. After the reaction, the solvent was removed in vacuo at 50° C. overnight. The resulting powder was divided into small portions of approx. 500 mg which were cast into rectangular bars at 150° C. for 30 minutes at a pressure of 4 MPa (40 bar).

[0084] The MWCNT/PK-Fu nanocomposite was further cross-linked with B-Ma through a reversible Diels-Alder reaction and characterized by DSC (FIG. 14). The thermograms show a wide endothermic transition in the temperature range between 120° C. and 180° C. for each consecutive thermal cycle, corroborating the reworkable nature of the nanocomposite reinforced with the bismaleimide additive.

[0085] The DMTA analysis carried out on rectangular bars of the nanocomposite reinforced with the bismaleimide additive shows excellent properties of the softening point (peak in tan (6)), loss moduli and elastic properties (FIG. 15).

[0086] In particular, the softening point (tan (6)) is 140° C. for the nanocomposite, which, after being subjected to resistive heating, increased to approx. 155° C. which would lead to a higher crosslinking density of the nanocomposite during resistive heating, without adhering to any theory. Elastic modulus (E’) and softening temperature (tan (6)) improve significantly after resistive heating for 24 h at 35 V.

[0087] FIG. 16 indicates that the impedance (that is, the total resistance of the material) of the nanocomposite reinforced with the bismaleimide additive reduces its impedance by half and becomes more electrically conductive with annealing, without adhering to any theory. SEM micrographs show the newly broken surfaces of the composite material after molding

[0088] (FIG. 17, arrows A and C), beams of MWCNT can be observed (indicated by white arrows). After resistive heating (FIG. 17, arrows B and D), the MWCNTs are better distributed, confirming the ability of electric current to restore a more effective percolative network to conduct electricity.

Example 4: Formation of Nanocomposites with Exfoliation of Graphite in Graphene Particles

[0089] In another specific embodiment of the invention, heating a polymer derivatized with furanyl groups at 70° C. produces a viscous mixing with graphite microparticles (20 μm) with a mass ratio of 80% polymer and 20% graphite in a conventional reactor provided with a mechanical mixer with adjustable speed. During mixing, the exfoliation of the 20 μm graphite occurs in graphene-like nanostructures, obtaining particle sizes of 200 nm. The exfoliation of the graphite occurs due to the anchoring of the furanyl groups of the polyketone on the graphite structure of the graphite with micrometer size through the Diels-Alder reaction and, by means of shear force in the conventional reactor, the polyketone releases sheets graffiti in a continuous process transforming the micrometric graffiti structure into another nano-sized graffiti structure. After subsequent cooling to room temperature, a composite matrix is produced that shows very good dispersion and stabilization of graphene-like nanostructures. The mixture exfoliated through the shear Diels-Alder reaction is then subjected to the retro-Diels-Alder reaction at 150° C. in N, N-dimethylformamide as solvent to separate the graphene-like structures from the polyketone. Once the separation process has been carried out, the exfoliation of the graphite is inferred with the naked eye by the lack of precipitation of the graphite powder and, analytically, by verifying the presence of nano-sized structures in the mixture by the light scattering technique. dynamic (DLS) (FIG. 7). The sequential process of Dials-Alder chemical anchoring of the polymer to the graphite microstructure, the exfoliation of the graphite in graphene structures and subsequent de-anchoring of the polymer from the exfoliated structure through the retro-Diels-Alder reaction, can be developed continuously to continue with the exfoliation of the resulting graphene-type nanostructures in order to obtain graphene sheets.

[0090] In this way, it is shown that the polymeric matrix has a strong exfoliating effect on the filling of graphite, and endorses the ability of polyketone as a useful agent to exfoliate graphene nanostructures in situ from bulk graphite and its subsequent use in the manufacture of functional materials.

Example 5: Preparation of a First Thermoconductive Monolithic Material

[0091] A monolithic thermoconductive material activated by electricity was obtained from the functional nanocomposite obtained in example 4, both using solvents with a solute mass of 10% of the functional nanocomposite obtained in example 4, and by mechanical mixing without solvents, drying, grinding, and subsequent compression molding at 150° C. and 4 MPa. Once the material was connected to a 25 Volt electrical circuit, its usability to irradiate heat by resistive heating could be verified (FIG. 8).

Example 6: Preparation of a Second Thermoconductive Monolithic Material

[0092] A thermoconductive monolithic material was obtained from the functional nanocomposite obtained in example 3, both using solvents with a mass of 10% of the solute, as well as by mechanical mixing without solvents at 70° C., drying, grinding, and subsequent compression molding at 150° C. and 4 MPa. Once the compound is broken, the pieces are put in contact and activated with temperature to achieve the retro-Diels-Alder reaction sequence using 150° C. to achieve the meeting of the material and subsequent annealing at 50° C. to achieve chemical self-repair. by the Diels-Alder reaction. It was found that the pieces of composite materials could be self-assembled to generate a single self-repairing monolithic structure (FIG. 6).

Example 7: Preparation of Monolithic Material with Wood Filler

[0093] A monolithic material was obtained by mixing the functional nanocomposite obtained in Example 4 with a mass of 20% and sawdust particles with a mass of 80%, in a conventional reactor equipped with a mechanical mixer with adjustable speed at 70° C., both using solvents with a 50% solute mass, as well as mechanical mixing without solvents and powder mixing without temperature, drying, grinding, and subsequent compression molding at 150° C. and 4 MPa. The resulting material is a wood-filled composite that conducts electricity (FIG. 10A and 1013).

Example 8. Preparation of Monolithic Material, Self-repairing with Electricity

[0094] A monolithic material self-repairing with electricity was obtained from the functional nanocomposite obtained in example 3 and example 4, both using solvents with a mass of 10% solute, and by mechanical mixing without solvents at 70° C., drying, grinding, and subsequent compression molding. A mechanical crack was made in the material and, once it is connected to a 25 Volt electrical circuit, it was verified that the material heats up, softens locally and self-repairs the mechanical damage (FIG. 5A, 5B, 5C and FIG. 11).

Example 9. Preparation of Functional Nanocompound Additive

[0095] An additive was obtained from the functional nanocomposite obtained in example 4 with a mass of 20%, which, mixed with asphalt bitumen with a mass of 80%, both using solvents with 10% solute and by mechanical mixing without solvents at 70° C., drying, grinding, and subsequent compression molding at 150° C. and 4 MPa, was characterized by rheology, determining an increase between 6 to 8 times the rheological properties of bitumen asphalt (FIGS. 12A and 12B).