process for producing a composition, composition, composite

专利摘要:
PROCESS FOR THE PRODUCTION OF A COMPOSITION, COMPOSITION, COMPOSITE A process for the production of a composition comprising one or more conductive nanocharges, one or more polyarylethersulfone (A) thermoplastic polymers, one or more uncured thermosetting resin precursors (P) and optionally one or more curing agents therefor, wherein said process comprises mixing or dispersing a first composition comprising one or more conductive nanocharges and one or more thermoplastic polyarylethersulfone polymers (A) with or in one or more precursors of uncured thermosetting resin (P) and, optionally, one or more curing agents for them.
公开号:BR112014011614B1
申请号:R112014011614-8
申请日:2012-12-19
公开日:2020-12-29
发明作者:Carmelo Luca Restuccia；Fiorenzo Lenzi；Emiliano Frulloni；Natalie Denise Jordan；Mark Edward Harriman
申请人:Cytec Technology Corp；
IPC主号:

专利说明:

[0001] The present invention relates to dispersions of conductive nanocharges (particularly conductive carbon-based nanocharges) in polymeric matrices (particularly epoxy resin systems) and composites produced from them and methods for their production. The present invention also relates to an improved method for dispersing these nanocharges in polymeric matrices and in composite structures through the use of a soluble thermoplastic polymer to release the nanocharges in the polymeric matrix. The present invention also relates to composite materials and structures having improved electrical and electromagnetic performance.
[0002] Composite materials comprising polymer resins and fillers are well known as structural materials for their ability to absorb loads and stresses and offer advantages over metals and ceramics where polymer composites are light, easier to manufacture and quickly adapted for specific applications and have high specific stiffness and strength and a low coefficient of thermal expansion. However, the application of these materials to primary and secondary structures of modern aircraft presents special challenges due to the dielectric nature of the resin matrix. Composite materials and / or structural modifications are generally required to meet the stringent functional and certification requirements for these components in terms of electrical and electromagnetic (EM) properties.
[0003] Primary structures for modern aircraft must provide capacity for protection from lightning, potential discharge, electrostatic dissipation (ESD), electromagnetic interference (EMI), electrical grounding and electromagnetic shielding. For a carbon fiber-reinforced polymer material to achieve these characteristics, it is necessary to achieve a homogeneously conductive material capable of ognjqtct c fkuukrc> «q fg ectico Cnfio fkuuq. q wuq ocku tgegpVg fg “ocVgtkcku fg Vgtegktc igtc>« q ”pgss structures mean that improvements are needed to the conductivity of the composite's z direction to avoid possible catastrophic accidents caused by the ignition of fuel vapors in the aircraft's wing tanks as a result of a lightning event. Eqpfotog wucfq cswk. “Fktg>« q z ”tghgtg is in the direction orthogonal to the planes in which the reinforced fibers are arranged in the composite structure or the axis through the thickness of the composite structure.
[0004] Thus, composite structures with adjusted electromagnetic properties are necessary in several applications where it is necessary to control the propagation, reflection, absorption and transparency of EM radiation. Aircraft composite structures require high efficacy of electromagnetic shielding to reduce disturbances caused by external sources, such as lightning, high intensity irradiation fields (HIRF) and electromagnetic pulses (EMPs) on board systems. The main protection mechanism in aircraft structures is reflection and efficiency is usually a function of electrical conductivity. Composite structures with EM radiation absorbing properties are also needed for unobservable structures and components used in aircraft, warships, submarines, missiles and wing turbine blades. The state of the art in radar absorbing materials (RAMs) is generally based on polymeric compounds containing high loads of relatively heavy metals or alloys.
[0005] An alternative approach can be based on single- or multi-layer radar absorbing structures (RAS) designed to reduce the reflection of EM radiation through destructive interference mechanisms. Typical examples of this class of structures are Dallenbach layers, Salisbury screens and Jaumann layers.
[0006] The reflectivity can be reduced by projecting structures with specific thicknesses using materials with adapted complex permeability (o) and permittivity (g) properties.
[0007] The ability of a material to absorb energy is a function of the ratio between the real and imaginary parts, or, equivalently, of the tangents of loss, according to the following expression:

[0008] For dielectric material modified by conductive charges, the absorption capacity can be enhanced by modifying its complex permittivity, which in microwave frequencies is closely related to electrical conductivity.
[0009] Carbon nanotubes (CNTs) are a class of conductive charges that can be used to modify electrical and electromagnetic characteristics due to their low densities, excellent electrical conductivity, as well as excellent mechanical properties, high thermal conductivity and high thermal stability. However, the use of CNTs in composite materials is limited due to problems in effectively dispersing them in the composite matrix, which is critical for improving matrix conductivity and doing so without compromising thermomechanical performance. The appearance of electrical conductivity in a CNT composite occurs when wo eqpVgúfq fg ectic etivkeq * tgfgtkfq eqoq ‘Ikokct fg rgteqnc>« q ”+ fi is reached and the conductive loads form a conductive path. As used here, the percolation threshold is the charge content to achieve conductivity values in direct current (DC) conditions equal to or greater than 10-6 S / m.
[00010] Several attempts have been made to make CNTs compatible and dispersed in polymeric matrices. US-2004/0186220-A discloses a method for compatibilizing and dispersing high contents of single-walled carbon nanotubes (SWCNTs) in electrically insulating matrices using a solvent-assisted procedure, and fabricating fibers, films and composite solids using a polymer coating / wrapping process. US-2010/0009165-A, US-2008/0194737-A, US-2008/0187482-A and US-2006/0054866-A describe the functionalization of CNTs in a form fg “p« q gpvolvkmgptq ”wucpfq rqniogtqu eqpjwicfqu fWpekqcc eqoq polyarylene ethylenes, which are then dispersed in thermoplastics and thermosets. WO-2010/007163-A reports the use of a CNT-modified binder to coat structural fibers in composite structures, which aims to solve manufacturing problems linked to the viscosity of highly loaded CNT systems, especially for infusion applications. US-2009/0298994-A discloses a process for dispersing CNT in a polyolefin matrix comprising the in situ polymerization of a polyolefin on the surface of the nanocharge and the subsequent dispersion of the material obtained in the matrix. US-2010/0189946-A reports the use of a combination of linear and functionalized / grafted fluorinated polymers that make CNTs compatible in polymer matrices. US-2009/0176924-A discloses a method for producing powdery master batches of highly concentrated CNT in various polymers. WO-2009/147415-A reports a material comprising at least one thermosetting resin, carbon-conducting additive materials and at least one thermoplastic polymer resin that dissolves in the resin and separates the phase after curing. In addition, there are a number of commercially available, but relatively expensive, CNT products in which CNT is pre-dispersed in a resin precursor system, for example, master batches of CNT / epoxy, which are reported as likely to achieve optimal dispersion levels. in an epoxy or epoxy mixing resin system.
[00011] There is still a need for an effective and economical method to disperse conductive carbon-based nanocharges in structural polymeric matrices, particularly epoxy resin, and other thermosetting resin systems, to modify or improve the properties of these polymeric matrices, particularly conductivity electrical power and permissiveness. In addition, there is still a need to disperse these nanocharges in such polymeric matrices without reassembly or segregation during processing and curing. In addition, there is still a need to increase the concentration of conductive carbon-based nanocharges in these structural polymeric composites and composites without adversely affecting their processing capacity and thermomechanical performance. The object of the invention is to satisfy one or more of these needs.
[00012] The present invention provides a process for producing a composition comprising one or more conductive nanocharges, one or more polyarylethersulfone thermoplastic polymers (A), one or more uncured thermosetting resin precursors (P) and, optionally, a or more curing agents therefor, wherein said process comprises mixing or dispersing a first composition comprising one or more conductive nanocharges and one or more polyarylethersulfone thermoplastic polymers (A) with or in one or more uncured thermosetting resin precursors ( P), and optionally one or more curing agents for them.
[00013] The present invention further provides several compositions, described below.
[00014] Accordingly, in a first aspect of the invention, a composition is provided comprising one or more conductive nanocharges, particularly conductive carbon based nanocharges and one or more polyarylethersulfone (A) thermoplastic polymers.
[00015] In the composition of the first aspect of the present invention, the nanocharge is coated or surrounded with one or more molecules of the thermoplastic polymer (A). The interaction between the nanocharge and the polyarylethersulfone does not depend, and it is believed that it does not involve covalent bonds or other chemical bonds between them. Instead, the chemical structure and end groups of polyarylethersulfone are able to interact with the electronic structure of the nanocharge to provide non-covalent association. It is the contention of the inventors that the specific sequence of strong electron withdrawing groups (- SO2-) and strong donating groups (-O-) on the molecular scale facilitates the electronic interaction between the polymer and the nanocharge, resulting in high dispersion of nanocharge, high load transfer and high conductivity. It is believed that the interaction between the polymer and the nanocharge is facilitated by the interaction of r electrons.
[00016] Q Vgtoq "tgxguVkogpVq" qw "gpxqnxkogpVq" tgfetg the polyarylethersulfone macromolecules are in contact with, or in association with, the nanocharger surface and include the polyarylethersulfone macromolecules that cover all or part of the surface. In modalities where the nanocharge is a nanotube, the surface coated or surrounded with the polyarylethersulfone molecules is the outer surface. The Vgtoq “tgxguVkogpVq” qw “gpxqnxkogpVq” p «q ug fguVkpc c eqpfgtkt cniwoc regularity or symmetrical configuration for the arrangement of the polyarylethersulfone macromolecules on the nanocharger surface.
[00017] In a preferred embodiment of the invention, at least a part of the conductive nanocharge must be dispersed, or coated or wrapped with the thermoplastic polymer before mixing or contacting the thermosetting resin precursors. Thus, the compositions of the first aspect of the invention do not comprise precursor (s) of uncured thermosetting resin (s).
[00018] The composition comprising nanocharge wrapped with polyarylethersulfone allows the release, manipulation and dispersion of the nanocharges in polymeric thermosetting matrices for the manufacture of composite materials with improved properties. The use of polyarylethersulfone reaches higher levels of processing capacity and dispersion of the nanocharge in the resin, without re-agglomeration of the nanocharge and, therefore, higher levels of electrical conductivity and permissiveness in the composite. The dispersion level can be monitored by microscopic techniques, such as high resolution Field Emission Scanning Electron Microscopy (FEG-SEM) or Transmission Electron Microscopy (TEM). In the present invention, the conductive nanocharge is suitably dispersed throughout the cured composition or composite, and where the precursors of thermoset resin and thermoplastic polymer have undergone phase separation during curing, the conductive nanocharge is appropriately present in (or otherwise associated with) ) thermoplastic polymer phase and thermosetting resin matrix phase. As noted here, the thermoplastic polymer appropriately undergoes phase separation from the thermosetting resin matrix after curing, resulting in the morphology of the micrometric or submicrometric particles and in the resulting cured resin, the conductive nanocharge is dispersed homogeneously throughout the polymer phase. thermoplastic and in the thermosetting resin matrix phase. Thus, the cured resins of the present invention can be differentiated from systems in which, after phase separation, substantially all (that is, at least 90% by weight) the conductive nanocharge is present in the thermosetting matrix phase (or the non-thermoplastic phase).
[00019] An advantage of the invention is that the high electrical conductivity and permittivity are obtained without any intermediate purification step or functionalization or dispersion of the nanocharge, that is, commercially available industrial grades of nanocharge with a relatively low C purity (90%) can be dispersed directly in the polyarylethersulfone thermoplastic without pretreatment. As shown below, multi-wall CNTs (MWCNTs; such as Nanocyl NC7000 grade (Belgium)), with a purity as low as 90% C purity can be used without the need for additional purification and / or functionalization processes. An additional purification step usually increases C purity by more than 95% (like the Nanocyl NC3100 MWCNT series). A functionalization step can include functionalization of -COOH for example (such as Nanocyl NC3101 MWCNT grade, which also has a C> 95% purity).
[00020] Furthermore, an additional advantage of the invention is that high electrical conductivity and permittivity are obtained without resorting to master batches of commercially expensive single wall CNT-epoxy or high purity (> 95%) CNTs. Instead, the invention provides high electrical conductivity and permittivity using low-cost, low-purity, multi-wall CNTs.
[00021] Thus, in one embodiment of the present invention, CNTs are relatively low-purity multi-wall CNTs (no more than 95% C purity and preferably at least about 90% C purity), which are preferably non-functionalized .
[00022] Furthermore, an additional advantage of the invention is that it allows for safer handling and better dispersion control of high CNT content in resin and composite systems using conventional resin mixing and pre-aggregation processes and equipment.
[00023] The composition of the first aspect of the invention preferably comprises the conductive nanocharge (CNF) in an amount such that the mass fraction w (CNF) is from about 0.1% to about 30%, preferably from about 0.1% to about 20%, from about 0.1% to about 19%, from about 0.1% to about 15%, preferably from about 1% to about 10% and usually from about 3% to about 8%, where w (CNF) is calculated as: w (CNF) = m (CNF) / (m (A) + m (CNF)), where m (CNF) is the mass of the conductive nanocharge in the composition, in (A) is the mass of the thermoplastic polymer (A) in the composition.
[00024] The compositions of the first aspect of the invention can take various physical forms, as is conventional in the art, including pelletized products, micronized particulate products, continuous or cut fibers, fibrous materials, woven and non-woven fabrics. Preferably, the composition of the first aspect of the invention is not a powdery composition, that is, it is not in powder form.
[00025] In one embodiment, the composition of the first aspect of the invention is in pelletized form, pellets being prepared by mixing the nanocharge in the melted thermoplastic polymer, for example, using a conventional melt extrusion process in a single screw extruder or double. The thermoplastic polymer and nanocharge can be fed into the extruder simultaneously or sequentially and is preferably a homogeneous physical mixture of nanocharge and polymer. The temperature inside the extruder should be appropriate for optimal thermoplastic rheology inside the extruder and is normally in the range of about 230 ° C, to about 400 ° C. A variable temperature profile can be used along the length of the extruder. The extruder can be equipped with threads having conventional high or low shear / mixture profiles, or a combination of them depending on the type and content of the load and on the rheological behavior of polymers. In one embodiment, a sequence of conventional low shear mixing screw sections can be used to achieve satisfactory levels of dispersion. In a preferred embodiment, the extruder is equipped with a high shear thread profile comprising conventional mixing segments associated with chaotic mixing units to create the best balance between shear forces and pressure in the barrel, optimizing dispersion levels, and these Process conditions can be achieved by using a Prism TS24HC extruder equipped with a 24mm corrective double thread system with an LD ratio of 40 to 1. Two different feed systems with different feed threads to suit different materials ( polymer pellets or nanocharges). A screw speed of approximately 200-300 RPM and a specific temperature profile in the various heating zones to achieve a maximum torque of 60-95% can be developed for a given mixture.
[00026] In a preferred embodiment, the composition of the first aspect of the invention is in micronized particulate form, since this increases the dispersion capacity in the thermosetting resin matrix and reduces the re-agglomeration of the nanocharge. The micronized paricyclic form is generally obtained from the pelleted and / or extruded form of the composition. Micronization can be carried out according to known conventional techniques, for example, rotary impact grinding, rotoplex grinding, rotating classifier grinding, ball grinding, counterex grinding, opposite fluidized bed jet grinding, spiral flow grinding , cryogenic grinding. In a preferred embodiment, a cryogenic grinding system (for example, an Alpine system) equipped with different rotary grinding media is used. A sequence of steps using staking discs, beaters, oscillating beaters and plate beaters can be developed to achieve micronized particles with an average particle size distribution (d50) in the range of about 5 to about 300 μm, preferably from about 10 to about 150 μm, more preferably about 20 to about 90 μm.
[00027] In another preferred embodiment, the composition of the first aspect of the invention is in the form of a fiber, film, or woven or non-woven, mat, textile or veil or the like, as disclosed in US-2006/0252334, the disclosure of which is incorporated as a reference. The fiber may be in the form of spun yarn monofilaments, extruded yarns, fused yarns, continuous yarns, continuous fibers, bi or multi-component fibers, random fibers, staple fibers, cut fibers, Swiss, filaments and hollow fibers and combinations of themselves. The fiber can be a yarn composed of multiple monofilaments or single and multiple monofilaments. Microfibers can have more complex structures, such as sheath / core, side / side, pie segments, islands-in-a-sea and can be made of different polymers or mixtures of them. Polymer microfibers can contain additional organic or inorganic fillers or modifiers.
[00028] The composition can be in the form of bands, ribbons, veils, fleece and combinations thereof, as well as in combinations with the fibrous forms mentioned above. Preferably the fiber (or yarn) comprises fibers each having a diameter of no more than about 100μm. Preferably a fiber or filament has a diameter d, or is a film, ribbon or loop having a thickness t, where d or t are in the range of up to and including about 100μm, preferably from about 1 to about 80 μm, more preferably from about 10 to about 50 μm. A veil is preferably supplied with dimensions of about 2cm to about 500cm in width, preferably preferably about 50cm to about 200cm in width. A veil made from the composition of the first aspect of the invention is particularly suitable for interposing between adjacent screens of, and in contact with, structural reinforcing fibers (such as carbon fibers) in one embodiment, particularly an embodiment that is suitable for use in resin infusion technology which is discussed later. Appropriate methods for preparing such fibers, films, nonwovens and veils and the like are disclosed in US-2006/0252334, the disclosure of which is incorporated by reference.
[00029] A woven fabric or textile comprising a fiber made from the composition of the first aspect of the invention includes a hybrid fabric further comprising reinforcing agent fibers such as carbon fiber, including cushioned reinforcing fibers. Examples of such fabrics include textiles containing resin-soluble fiber commercially available as PRIFORMTM (Cytec Engineered Materials).
[00030] The compositions of the first aspect of the invention can also be prepared by a process (referred to herein as in situ polymerization) in which the conductive nanocharge is present during the synthesis of the thermoplastic polymer. The reaction mixture can simply be contacted, optionally in the presence of any catalyst, with the nanocharge before the polymerization reaction starts or during the polymerization reaction. Thus, the nanocharge can simply be introduced into the polymerization reaction vessel, so that the nanocharge is present in its entirety at the start of the reaction, or the nanocharge can be introduced or contacted with the reaction mixture continuously or in portions as the reaction occurs. For example, an in situ polymerization process may comprise the steps of: (i) preparing a suspension of the conductive nanocharge in an inert solvent; and (ii) prepare a reaction mixture from the nanocharge suspension and optional catalyst by adding the monomeric reagents and conducting the polymerization reaction.
[00031] The in situ polymerization reaction may involve the polymerization of the thermoplastic polymer on or on the surface of the conductive nanocharge and bring about a more effective coating or wrapping of the conductive nanocharge with the thermoplastic polymer. In addition, in situ polymerization can improve the dispersion of the nanocharge in the thermoplastic polymer and reduce the tendency for subsequent re-agglomeration. The coated nanocharge particles are recovered from the reaction mixture using conventional techniques and can be pelleted, micronized or processed in another normal way.
[00032] Thus, in a second aspect, the present invention provides a process for the production of a composition comprising the conductive nanocharge and one or more polyarylethersulfone thermoplastic polymers (A) as described herein. In a preferred embodiment, the composition is prepared by mixing the nanocharge and the fused thermoplastic polymer (A), for example, in a double screw extruder, preferably using chaotic mixture and high shear profiles, optionally followed by micronization and dissolution in the formulation of thermosetting. In a preferred embodiment, polyarylethersulfone undergoes phase separation after curing resulting in morphology of micrometric or submicrometric particles. Surprisingly, the mechanical and thermal properties of the resulting resin are maintained or even improved. The polyarylethersulfone thermoplastic polymer (A)
[00033] The polyarylethersulfone thermoplastic polymer (A) comprises repeating units connected by ether, optionally also comprising repeating units connected by thioether, the units being selected from: - [ArSO2Ar] n- and optionally from: - [Ar] a- where: Ar is phenylene; n = 1 to 2 and can be fractional; a = 1 to 3 and can be fractional and when it exceeds 1, said phenylene groups are linearly linked through a single chemical bond or a divalent group other than -SO2- (preferably where the divalent group is a -C group (R9 ) 2- where each R9 can be the same or different and selected from H and C1-8 alkyl (particularly methyl)), or are fused together, as long as the repeating unit - [ArSO2Ar] n- is always present in the polyarylethersulfone in a proportion that on average at least two of said units - [ArSO2Ar] n- are in sequence in each polymer chain present, and in which the polyarylethersulfone has one or more reactive pendant and / or end groups.
[00034] Eqo “htaekqpáriq”, the refereepe fi fekVa aq xanqr ofifkq rare a given polymer chain containing units having various values of n or a.
[00035] In one embodiment, the phenylene groups on the polyarylethersulfones are linked through a single bond.
[00036] The phenylene groups on the polyarylethersulfones can be substituted by one or more substituent groups, each independently selected from C1-8 saturated or unsaturated branched or linear aliphatic aliphatic groups or fractions optionally comprising one or more heteroatoms selected from O, S , N, or halo (for example, Cl or F); and / or groups that provide active hydrogen especially OH, NH2, NHRa or -SH, where Ra is a hydrocarbon group containing up to eight carbon atoms, or that provide other cross-linking activities especially benzoxazine, epoxy, (meth) acrylate, cyanate, isocyanate, acetylene or ethylene, as in vinyl, allyl or maleimide, anhydride, oxazoline and monomers containing unsaturation.
[00037] Preferably, the phenylene groups are meta or para (preferably para). A mixture of conformations (particularly meta and para conformations) may be present along the structure of the polymer.
[00038] Preferably the polyarylethersulfone comprises a combination of repeating units - [ArSO2Ar] n- and - [Ar] a-, linked by ether and / or thioether bonds, preferably by ether bonds. Thus, preferably polyarylethersulfone comprises a combination of repeating units linked by polyethersulfone ether (PES) and polyetherethersulfone (PEES).
[00039] The relative proportions of repetition units - [ArSO2Ar] n- and - [Ar] a- are such that, on average, at least two repetition units - [ArSO2Ar] n- are in immediate mutual succession in each chain of polymer present and the ratio of units - [ArSO2Ar] n- to units - [Ar] a- is preferably in the range of 1:99 to 99: 1, more preferably 10:90 to 90:10. Typically, the ratio [ArSO2Ar] n: [Ar] a is in the range of 75:25 to 50:50.
[00040] In one embodiment, the preferred repeat units on polyarylethersulfones are: (I): -X-Ar-SO2-Ar-X-Ar-SO2-Ar- (referred to here as a “wpkfcfg RGU” + and (II ): -X- (Ar) aX-Ar-SO2-Ar- (referred to here as a “wpkfcfg RGGU” + where: X is O or S (preferably O) and may be different between units; and the ratio of units I: II is preferably in the range of 10:90 to 80:20, more preferably in the range of 10:90 to 55:45, more preferably in the range of 25:75 to 50:50, and in one embodiment, the ratio I: II is in the range of 20:80 to 70:30, more preferably in the range of 30:70 to 70:30, more preferably in the range of 35:65 to 65:35.
[00041] The preferred relative proportions of the repeat units of a polyarylethersulfone can be expressed as a function of the weight percent SO2 content, defined as 100 times (weight of SO2) / (average weight of the repetition unit). The preferred SO2 content is at least 22, preferably 23 to 25%. When a = 1 this corresponds to the PES / PEES ratio of at least 20:80, preferably in the range 35:65 to 65:35.
[00042] The flow temperature of polyetherethersulfone is generally lower than that of a corresponding polyetheretherone Mn, but both have similar mechanical properties. In this sense, the ratio can be determined by determining the values for a and n above.
[00043] US-6437080 discloses processes for obtaining these compositions from their monomer precursors in order to isolate the monomer precursors at selected molecular weights as desired, and these disclosures are incorporated herein by reference.
[00044] The proportions above refer only to the units mentioned. In addition to these units, a polyarylethersulfone can contain up to 50 mol%, preferably up to 25 mol%, of other repeating units: the preferred SO2 content ranges, then apply to the entire polymer. These units can be, for example, of formula:
where L is a direct linker, oxygen, sulfur, -CO- or a divalent group (preferably a divalent hydrocarbon radical, preferably where the divalent group is a -C (R12) 2- group where each R12 can be equal to or different and selected from H and C1-8 alkyl (particularly methyl)).
[00045] When polyarylethersulfone is the product of nucleophilic synthesis, its units may be derived, for example, from one or more bisphenols and / or bistioles or phenol-vk „ku" eqttgurqpfgpvgu "ugngekqpcfqu" fg "jkftqswkpqpc." 6.6Ó- dihydroxybiphenyl, resorcinol, fkjkftqzkpchvcngpq "* 4.8" g "qwvtqu" ku »ogtqu +." 6.6Ó- fkjifrqzkdgnzqfgnqnc, 4. 4th-di (4-hydroxyphenyl) propane and -methane. If a bis-thiol is used, it can be formed in situ, that is, a dihalide can be reacted with a sulfide or polysulfide or alkali thiosulfate.
[00046] Other examples of these additional units are of formula:
go "swg" S "g" ONLY. "swg" rqfgo "kiwcku" qw "fkhgtgnvgu." u «q" EQ "qw SO2 = Cr 'fi wo tcfkecn ctqoávkeq fkxcngnVg g = gr fi 2. 3. 4 qw 5. eqnVcnVq swg r is not zero where Q is SO20 CtÓ fi rtghgtgnekcnognte at least one divalent aromatic radical selected from phenylene, biphenylene or terphenylene. Private units have the formula:
where q is 1, 2 or 3. When the polymer is the product of nucleophilic synthesis, these units can be derived from one or more dihalides, by gzgornq. "ugngekqpcfqu" fg "6.6Ó-dihalobenzophenona, biphenyl-6.6Ódku * 6- chlorophenylsulfonyl), 1,4, bis (4-jcnqdgpzqü + dgnzgpq g 6.6ó-bis (4-halobenzoyl) biphenyl, which can naturally be partially derived from the corresponding bisphenols.
[00047] Polyarylethersulfone can be the nucleophilic synthesis product of halophenols and / or halothiophenols. In any nucleophilic synthesis, halogen, whether chlorine or bromine, can be activated by the presence of a copper catalyst. This activation is often unnecessary if the halogen is activated by an electron withdrawing group. In any case, fluorine is generally more active than chloride. Any nucleophilic synthesis of a polyarylethersulfone is preferably carried out in the presence of one or more alkali metal salts, such as KOH, NaOH or K2CO3 in up to 10% molar excess over the stoichiometric.
[00048] As noted above, polyarylethersulfone contains one or more reactive pendant and / or end groups, and in a preferred embodiment polyarylethersulfone contains two of these reactive pendant and / or end groups. In one embodiment, polyarylethersulfone comprises one of such a pendant and / or reactive end group. Preferably, reactive pendant and / or end groups are groups that provide active hydrogen, particularly OH, NH2, NHRb or -SH (where Rb is a hydrocarbon group containing up to eight carbon atoms), or are groups that provide other activities of crosslinking, particularly benzoxazine, epoxy, (meth) acrylate, cyanate, isocyanate, acetylene or ethylene, with vinyl, allyl or maleimide, anhydride, oxazaline and monomers containing saturation. In one embodiment, the reactive pendant and / or end groups are of the formula -C '- [go swg C fi woc nkic> «q a divalent hydrocarbon group, preferably aromatic, preferably phenyl. Examples of Y are groups that provide active hydrogen, particularly OH, NH2, NHRb or -SH (where Rb is a hydrocarbon group containing up to eight carbon atoms), or groups that provide other cross-linking activity, particularly benzoxazine, epoxy, (met ) acrylate, cyanate, isocyanate, acetylene or ethylene, with vinyl, allyl or maleimide, anhydride, oxazaline and monomers containing saturation. Groups that provide other cross-linking activities can be linked to the Ar groups of the polyarylethersulfone through a direct bond, or through an ether, thioether, sulfone -CO- bond or divalent hydrocarbon radical as described above, most commonly through a bond ether, thioether or sulfone. In another embodiment, the end groups, but preferably no more than a relatively smaller proportion, can be selected from halo groups (particularly chlorine). Reactive end groups can be obtained by a reaction of monomers or by later conversion of polymer products before or after isolation. In a method for introducing the reactive pendant and / or end group, for example, using activated aromatic halides (for example, dichlorodiphenylsulfone) as the raw material for the polymer, the synthetic process uses a slightly larger amount than the stoichiometric aromatic activated halide and the resulting polymer having halogenated end groups is then reacted with an aminophenol (e.g., m-aminophenol) to create end amino groups.
[00049] The reactive pendant and / or end groups are / are preferably selected from groups that provide active hydrogen, particularly OH and NH2, particularly NH2. Preferably, the polymer comprises two such groups.
[00050] The average molar mass Mn of the polyarylethersulfone is suitably in the range of about 2,000 to about 30,000, preferably from about 2,000 to about 25,000, preferably from about 2,000 to about 15,000 and in an embodiment of about 3,000 at about 10,000 g / mol.
[00051] The synthesis of polyarylethersulfone is further described in US-2004/0044141 and US-6437080, and these disclosures are hereby incorporated by reference. The conductive nanocharge
[00052] Q Vetoq "pcpqectic eqpfwVqtc", eqpfotoe wucfq cswk. kpenwk. among others, components referred to in the art as carbon nanotubes (CNTs), including single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs) and multi-walled carbon nanotubes (MWCNTs), carbon nanoparticles, nanofibers carbon, carbon nanocords, carbon nanotubes, carbon nanofibrils, carbon nano needles, carbon nanofibers, carbon nanocons, carbon nanocones, carbon nanoparticles and carbon nano-ohms, as well as the respective boron nitride components. In an oqfcnkfcfe, q Vetoq "pcpqectic eqpfwVqtc" is used for conductive carbon-based nanocharges and includes, among others, the components dcugcfqu go ectdqpq fguetkVqu cekoc0 Q Vgtoq "pcpqectic eqpfwkqktnts and even cut fibers" / shorts, black carbon or a combination thereof with or without a full or partial metallic coating or other fullerene materials and combinations thereof.
[00053] Carbon nanotubes can be of any chirality. Carbon nanotubes can be armchair nanotubes. Nanotubes can be semiconductor nanotubes or any other type that has electrical conductivity.
[00054] Carbon nanotubes can be produced by chemical vapor deposition (CVD), catalytic chemical vapor deposition (CCVD), carbon catalyst vapor deposit (CCVD), high pressure carbon monoxide process (HiPco), arc discharge, laser vaporization or other methods known to those skilled in the art can also be used in the processes of the present invention.
[00055] The preferred nanocharge of the invention is the carbon nanotube, particularly the multi-wall carbon nanotube. Typically, carbon nanotubes are tubular, chain-like structures having outside diameters in the range of about 0.4nm to about 100nm. Preferably the outside diameter is not more than about 50 nm, preferably not more than about 25 nm, and in one embodiment it is not more than about 15 nm. Preferably, the outside diameter is at least about 1nm, and in an embodiment at least about 5nm.
[00056] The conductive nanocharge preferably has an aspect ratio of not more than 10,000: 1, preferably not more than 1000: 1. Preferably, the conductive nanocharge has an aspect ratio of at least 100: 1. The term aspect ratio used here is understood to refer to a ratio from the largest dimension to the smallest dimension of the three dimensions of the body. The polymeric thermosetting matrix
[00057] Eopfotog wucfq cswk. woc "eoorouk>« the fon roníogto ewtáxgn "refers to ug c woc eoorouk>" the cpVgu fc ewtc g woc "eoorouk>" the fg tgukpc fg vgtooewtc "tghgtg is a post-cured composition.
[00058] In a third aspect of the present invention, a thermosetting resin system or curable polymer composition comprising one or more conductive nanocharges, one or more polyarylethylsulfone (A) thermoplastic polymers and one or more non-thermosetting resin precursors is provided cured (P), and optionally one or more curing agents for them.
[00059] In a preferred embodiment, the thermosetting resin system or curable polymer composition of the third aspect of the invention comprises the nanocharge involved with polyarylethersulfone composition according to the first aspect of the invention defined here and one or more precursors of resin uncured thermosetting (P), and optionally one or more curing agents for them.
[00060] As noted above, it is preferred that at least a part of the conductive nanocharge should be dispersed, or coated or enveloped with the thermoplastic polymer before mixing or contacting the thermosetting resin precursors. Thus, the compositions of the third aspect of the invention can be obtained by: (i) mixing or dispersing a conductive nanocharge with or in a composition comprising one or more thermoplastic polyarylethersulfone polymers (A) and one or more uncured thermosetting resin precursors (P), and, optionally, one or more curing agents for them; or (ii) in a preferred embodiment, mixing or dispersing a composition according to the first aspect of the invention with or in one or more uncured (P) thermosetting resin precursors, and, optionally, one or more curing agents for them; or (iii) still in a preferred embodiment, mixing or dispersing a composition according to the first aspect of the invention with or in a composition comprising one or more uncured thermosetting resin precursors (P) and further comprising one or more polyarylethersulfones as defined here (same or different for the polyarylethersulfones in the composition of the first aspect) and one or more conductive nanocharges as defined here (same or different for the nanocharge in the composition of the first aspect), and, optionally, one or more curing agents for them.
[00061] When a curing agent is present, the composition of the third aspect of the invention is preferably obtained by adding the curing agents, after mixing said one or more uncured thermosetting resin precursors (P), one or more polyarylethersulfones and conductive nanocharges.
[00062] In a fourth aspect of the invention, there is provided a cured thermosetting resin composition (R) derived from the composition as defined for the third aspect of the invention comprising one or more conductive carbon-based nanocharges, one or more polyarylethersulfone thermoplastic polymers ( A) and one or more uncured thermosetting resin precursors (P), and optionally one or more curing agents therefor.
[00063] In a preferred embodiment, the composition of the fourth aspect of the invention is derived from a composition comprising nanocharge involved with polyarylethersulfone defined herein and one or more uncured (P) thermosetting resin precursors, and, optionally, one or more agents healing for them.
[00064] During processing, the thermoplastic dissolves in the resin system before the resin system's coagulation point and provides a well-dispersed network of nanocharge at the molecular level, without re-agglomeration. This network provides a significant increase in the electrical conductivity and permittivity of the resin matrix and the composite material formed using this matrix.
[00065] The present invention is concerned mainly with thermosetting epoxy resins derived from one or more epoxy resin precursors. The epoxy resin precursor preferably has at least two epoxide groups per molecule, and can be a polyfunctional epoxide having three, four or more epoxide groups per molecule. The epoxy resin precursor is suitably liquid at room temperature. Suitable epoxy resin precursors include the mono- or polyglycidyl derivative of one or more of the group of compounds consisting of aromatic diamines, aromatic monoprimary amines, aminophenols, polyhydric phenols, polyhydric alcohols, polycarboxylic acids and the like or a mixture thereof.
[00066] Preferred epoxy resin precursors are selected from:
[00067] bisphenol A, bisphenol F, dihydroxydiphenyl sulfone, dihydroxybenzophenone and dihydroxy diphenyl glycidyl ethers;
[00068] epoxy resins based on Novolacs; and
[00069] glycidyl functional reaction products of m- or p-aminophenol, m- or p-phenylene diamine, diamine 2,4-, 2,6 or 3,4-toluylene fkcokpc. "5.5Ó- qw" 6.6Ó- diaminodiphenyl methane, particularly where the epoxy resin precursor has at least two epoxide groups per molecule.
[00070] Particularly preferred epoxy resin precursors are selected from bisphenol A diglycidyl ether (DGEBA); the bisphenol F diglycidyl ether (DGEBF); O, N, N-triglycidyl-para-aminophenol (TGPAP); O, N, N-triglycidyl-meta-cokpqhgpqn "* VIOCR + =" g "PPPÓ.PÓ-tetraglycidyl diaminodiphenyl methane (TGDDM). In one embodiment, epoxy resin precursors are selected from DGEBA and DGEBF. In a preferred embodiment, precursors of epoxy resin are selected from DGEBF and TGPAP and mixtures thereof.
[00071] The ratio of epoxy group equivalent to amino hydrogen is preferably in the range of 1.0 to 2.0. Formulations exhibiting an excess of epoxy are preferred for accurate stoichiometry.
[00072] Commercially available epoxy resin precursors crtqrtkcfqu rctc wuq pc rtgugpVg kpxgp> «q PPpo.po-tetraglycidyl diamino diphenylmethane (for example, MY 9663, MY 720 or MY 721 series; Jwpvuocp + = PPPÓ.P. (4-aminophenyl) -1,4-di-iso-rtqrüdgpzgpq * rqt gzgornq GRQP 3293 = OqogpVkxg + = PPpó.pó- tetraclycidyl-bis (4-amino-3,5-dimethylphenyl) -1,4-di- isopropylbenzene, (for example, EPON 1072; Momentive); p-aminophenol triglycidyl ethers (for example, MI 0510; Hunstman); m-aminophenol triglycidyl ethers (for example, MI 0610; Hunstman); materials based on diglicidyl ethers of bisphenol A as 2,2-dku * 6.6Ó-dihydroxy phenyl) propane (for example, DER 661 (Dow), or EPON 828 (Momentive) and Novolac resins preferably with viscosity 8-20 Pa at 25 ° C; glycidyl ethers of Novolac phenol resins (eg DEN 431 or DEN 438; Dow); Novolac phenolic based on cyclopentadiene (eg Tactix 556, Huntsman); diglycidyl 1,2-phthalate (eg GLY CE L A-100); diglycidyl derivatives of dihydroxy diphenyl methane (Bisphenol F) (e.g., PY 306; Huntsman). Other precursors fg tgukpc gr „zk kpelugo ekelqclkfaVkequ eqoq 5 ', 6ó-epoxycyclohexyl-3,4-epoxycyclohexane carboxylate (for example, CY 179; Huntsman).
[00073] In an embodiment of the present invention, the thermosetting resin system or curable polymer composition comprises a mixture of epoxy resin precursors having the same or different functionality (where the Vgtoq "fupekqpclkfcfg" pguVg eqpVgzVq ukipkfíec q púogtq fg itwrqu gr „Functional zkfq). The mixture of epoxy resin precursors may comprise one or more epoxy resin precursors with two epoxide groups per molecule (hereinafter referred to as P2 precursors), and / or one or more epoxy resin precursors with three epoxide groups per molecule (hereinafter referred to as precursors P3), and / or one or more precursors of epoxy resin with four epoxide groups per molecule (hereinafter referred to as P4 precursors). The mixture can also comprise one or more epoxy resin precursors with more than four epoxide groups per molecule (hereinafter referred to as PP precursors). In one embodiment, only P3 precursors can be present. In an alternative embodiment, only P4 precursors can be present. In one embodiment, a mixture of epoxy resin precursors comprises: from about 0% by weight to about 60% by weight of epoxy resin precursors (P2); from about 0% by weight to about 55% by weight of epoxy resin precursors (P3); and from about 0% by weight to about 80% by weight of epoxy resin precursors (P4);
[00074] In one embodiment, the mixture comprises only an epoxy resin precursor of a certain functionality, in the proportions mentioned above.
[00075] The thermosetting resin system or curable polymer composition of the invention is thermally curable. The addition of curing agents and / or catalysts is optional, but the use of these can increase the cure rate and / or reduce cure temperatures, if desired. In a preferred embodiment, one or more curing agents are used, optionally with one or more catalysts. In an alternative embodiment, the thermosetting resin system or curable polymer composition described here is thermally cured without the use of curing agents or catalysts.
[00076] Preferably, however, the thermosetting resin system or curable polymer composition comprises one or more curing agents. The curing agent is suitably selected from known curing agents, for example, as disclosed in EP-A-0311349, EP-A-0486197, EP-A-0365168 or in US-6013730, which are incorporated herein by reference, as a compound of amino acids with molecular weight up to 500 per amino group, for example, an aromatic amine or a derivative of guanidine. An aromatic amine curing agent is preferred, preferably an aromatic amine with at least two amino groups per molecule and particularly preferably diaminodiphenyl sulfones, for example, where the amino groups are in the meta- or para- position in tgnc> «q co itwrq swlhopc. Gzgornqu rttkewlctgs u'q 3,3'- and 4-.6'1- diaminodiphenylsulfone (DDS); methylenedianiline; bis (4-amino-3,5-dimethylphenyl) -1,4-diisopropylbenzene; bis (4-aminophenyl) -1,4-diisoprorkldgpzgpo = 6,6óogVklgpodks- (2,6-diethyl) -aniline (MDEA; Lonza); 6.6Óogvkngpqdku- (3-chloro, 2,6-diethyl) -aniline (MCDEA; Lonza); 6.6Óogvkngpqdku- (2,6-diisopropyl) -aniline (M-DIPA; Lonza); 3,5-diethyl toluene-2,4 / 2,6-diamine (D-GVFC: 2 = Nqnzc + = 6,6ooeVüenqdku- (2-isopropyl-6-methyl) -aniline (M-MIPA; Lonza); 4- chlorophenyl-N, N-dimethyl-urea (eg Monuron); 3,4-dichlorophenyl-N, N-dimethyl-urea (eg DiuronTM) and dicyandiamide (AmicureTM CG 1200; Pacific Anchor Chemical). of bisphenol, such as bisphenol-S or thiodiphenol, are also useful as curing agents for epoxy resins. They are suitable for curing agents. «q 5.50 - and 4-.6'1- DDS. also include anhydrides, particularly polycarboxylic anhydrides, such as naic anhydride, methylnadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride or trimellitic anhydride.
[00077] In one embodiment, the thermosetting resin system or curable polymer composition comprises one or more catalysts to accelerate the curing reaction. Suitable catalysts are well known in the art and include Lewis acids or bases. Specific examples include compositions comprising boron trifluoride, such as the etherates or amine adducts therefor (for example, the boron trifluoride and ethylamine adduct), particularly where epoxy resin precursors are used in conjunction with the aforementioned amine curing agents .
[00078] The curable polymer composition may comprise a curing agent and catalyst, for example, as disclosed in US-6265491, the contents of which are incorporated herein by reference.
[00079] The amount of thermoplastic polymer (A) combined with or added to the resin precursor is preferably such that the mass fraction w (A), calculated as w (A) = m (A) / m, where m ( A) is the mass of the thermoplastic polymer (A) present in the thermoset resin composition cured with mass m, from 0.5% to 40%, preferably from 1% to 35%, and more preferably from 2% to 30% .
[00080] The curing agent is normally present in about 1-60%, by weight of the combined total weight of the thermosetting resin precursors plus curing agent in the composition, preferably about 20-50% by weight, usually about 25-40% by weight.
[00081] Thus, the present invention provides a process for preparing cured thermosetting resin compositions (R), said process comprising the steps of
[00082] prepare nanocharges involved in thermoplastic, as described here;
[00083] mixing and / or dissolving said nanocharges wrapped with thermoplastic with one or more uncured thermosetting resin precursors (P), as described here; and
[00084] cure the mixture, for example, by dissolving / dispersing it in a curing agent / catalyst at reduced temperature and then curing. applications
[00085] The compositions described herein can be used to manufacture cast or molded structural materials and are particularly suitable for manufacturing impact-resistant or fiber-reinforced composite load structures. The compositions can be used neat, or as fiber or filler-reinforced composite materials. In some embodiments, the composition can be used to improve the electrical conductivity of the composite's z direction; in some other modalities the composition can be used to transmit the signature control characteristics to composite structures.
[00086] Thus, according to another aspect of the invention, there is provided a molded or molten article comprising the thermosetting resin compositions defined herein or derivable from the curable polymer compositions defined herein.
[00087] According to another aspect of the invention, a composite material is provided comprising, or derivable from, the thermosetting resin compositions or curable polymer compositions described above, particularly wherein the composite material is, or comprises, a pre-preg.
[00088] Molded products are obtainable from the compositions of the present invention by the general steps of mixing the conductive nanocharges involved with thermoplastic with one or more uncured thermosetting resin precursors (P), adding the curing agent and catalyst as necessary, homogenizing the mixture thus obtained, melting the mixture into a mold to obtain a molded product, and curing the molded product at an elevated temperature of at least 100 ° C to form a cured molded product.
[00089] In a preferred embodiment, particularly for the manufacture of load-resistant or impact-resistant structures, the compositions are composite materials further comprising reinforcing agents such as fibers or fillers.
[00090] The fibers can be added short or cut normally of the average length of the fiber no more than about 2 cm and, normally, at least about 0.1 mm, for example, about 6 mm. Alternatively, and preferably, the fibers are continuous and can, for example, be unidirectionally arranged fibers or woven, knitted or nonwoven knitted fabrics to form a pre-preg. As used here, q Vgtoq “rre-rrei” refers to pre-preg and composite materials with uncured reinforced fiber. A pre-preg usually comprises continuous fibers, but combinations of short and / or cut fibers and continuous fibers can be used. For some applications, pre-preg fibers can be selected from short unidirectional fibers and / or cut alone. Fiber reinforcement can be selected from mixed or hybrid fiber systems that comprise synthetic or natural fibers, or a combination thereof.
[00091] The fibers can be sized or not sized. The fibers can normally be added in a concentration of 5 to 35, preferably at least 20% by weight. For structural applications, it is preferable to use continuous fiber, for example, glass or carbon, especially at 30 to 70, more especially 50 to 70% by volume.
[00092] The fiber can be organic, such as aramid fibers, metallized polymer fibers (where the polymer can be soluble or insoluble in the resin matrix), polyphenol or inorganic terephthalamide fibers or a combination thereof. Among inorganic fibers, glass fibers such as "" G "," A "," G-ET "," E "," F "," T "," U "qw fkdras fg swcrtzq rqfgo sgt used, or alumina, zirconia, silicon carbide, metallized glass, other ceramic or metal compounds. A very suitable reinforcement fiber is carbon, especially as graphite. Graphite or carbon fibers can also be metallized (with continuous or discontinuous metal layers). Graphite fibers that have been found to be especially useful in the invention are those supplied by Cytec under the trade name T650-35, T650-42 and T300; those supplied by Toray under the trade name T800-HB; and those supplied by Hexcel under the trade name AS4, AU4, IM 8 and IM 7.
[00093] The organic fiber or carbon is preferably not dimensioned or is dimensioned with a material that is compatible with the composition according to the invention, in the sense of being soluble in the composition of the liquid precursor without adverse reaction or of binding to the fiber and to the thermoset / thermoplastic composition described here. In particular, carbon or graphite fibers that are not sized or are sized with resin precursor or polyarylethersulfone are preferred. The inorganic fiber is preferably sized with a material that binds to the fiber and the polymer composition; examples are organosilane coupling agents applied to glass fiber.
[00094] The thermoplastic polyarylethersulfone polymer (A) defined above functions as a compatibilizer for the conductive nanocharges in the thermosetting resin and a curing agent for the thermosetting resin. The compositions described herein may also contain additional curing agents such as homopolymers or copolymers, alone or in combination with polyamides, copolymides, polyimides, aramids, polyketones, polyethylketones (PEK), polyetherethylketones (PEEK), polyethylketonetones (PEKK), polyesters, polyurethanes polysulfones, polysulfides, polyphenylene oxide (PPO) and modified PPO, poly (ethylene oxide) (PEO) and polypropylene oxide, polystyrenes, polybutadienes, polyacrylates, polymethacrylates, polyacrylics, polyphenylsulfone, high-performance hydrocarbon polymers liquid, elastomers and segmented elastomers and the polyarylethersulfones defined above, particulate hardening agents, for example, preformed particles such as, polymer particles, ceramic particles, carbon particles, glass granules, metal and alloy particles, particles rubber and rubber coated glass beads, fillers such as polite trafluoroethylene, alumina, silica, calcium carbonate, calcium oxide, graphite, boron nitride, mica, talc and vermiculite, pigments / dyes, nucleating agents, wetting agents, flow control agents / viscosity modifiers, flame retardants , plasticizers, UV absorbers, antifungal compounds, viscosity agents, inhibitors and stabilizers such as phosphates. Liquid rubbers with reactive groups can also be used. The total of these materials and any fibrous reinforcing agent in a composition is usually at least 20% by volume, as a percentage of the total volume of the composition. The percentages of fibers and other materials are calculated on the total composition after the reaction or processing at the temperatures defined below. In one embodiment, the curing agents present in the composition comprise and preferably consist of high Tg designed thermoplastics, preferably the polyarylethersulfone thermoplastic polymers defined above.
[00095] Composites are obtained from a curable polymer composition made by combining the components of the curable polymer compositions described above with fiber reinforcing agent and / or other materials. For example, the manufacture of a pre-preg normally comprises the steps of mixing the modifier, the nanocharges involved with thermoplastic and the uncured thermosetting resin precursors (P), adding a curing agent and catalyst as needed, homogenizing the mixture as well obtained, and apply the homogenized mixture to a bundle or strand of fibers aligned in parallel or weft of fiber or braids or non-woven fabrics to form the pre-preg. A solvent may be present to aid processing. The solvent and its proportion are chosen so that the mixture of the components forms at least one stable emulsion, preferably an apparently monophasic stable solution. Usually a mixture of solvents is used, for example, from a halogenated hydrocarbon and an alcohol, in a ratio appropriately in the range of 99: 1 to 85:15. Conveniently, the solvents in this mixture should boil below 100 ° C at a pressure of 1 atm and should be mutually miscible in the proportions used. Alternatively, the components can be placed together by hot melt and / or high shear. The mixture is stirred until it is sufficiently homogeneous. Thereafter, any solvent is removed by evaporation. Evaporation is duly at 50-200 ° C and, at least in its final phase, it can be in subatmospheric pressure, for example, in the range of 13.33 Pa to 1333 Pa (0.1 to 10 mm Hg). The composition preferably contains up to 5% w / w of volatile solvent, to assist the flow when used to impregnate the fibers. This residual solvent will be removed in contact with the hot rollers of the impregnation machine.
[00096] More specifically, the manufacture of articles and composites of the compositions of the present invention is as follows. The composition in the form of a resin solution is transferred to a mold or tool suitable for the preparation of a panel, pre-preg or the like, the mold or tool having been preheated to a desired degassing temperature. The stable emulsion is combined with any materials or agents for reinforcement, hardening, loading, nucleation or the like, and temperatures are high to start curing. Proper curing is carried out at an elevated temperature up to 200 ° C, preferably in the range of 160 to 200 ° C, more preferably at about 170-190 ° C and using high pressure to restrict the effects of exhaust gas formation, or to restrict the formation of voids, appropriately at a pressure of up to 10 bar, preferably in the range of 3 to 7 bar abs. Appropriately, the curing temperature is reached with heating up to 5 ° C / min. For example, 2 ° C to 3 ° C / min and is maintained for the required period of up to 9 hours, preferably up to 6 hours, for example, 2 to 4 hours. The use of a catalyst can allow even lower curing temperatures. The pressure is released during the process and the temperature is reduced by cooling down to 5 ° C / min. For example, up to 3 ° C / min. Post-curing at temperatures in the range of 190 ° C to 200 ° C can be performed, at atmospheric pressure, using appropriate heating rates to improve the glass transition temperature of the product or otherwise. The mold or tool can be constructed of any suitable material, for example, an unsaturated polyester or thermosetting resin such as epoxy or bis-maleimides with a thermal resistance greater than the forming temperature to be employed. The reinforcement is suitably supplied in the form of glass fibers. Composite molds can be prepared in a conventional manner.
[00097] The composition, possibly containing a volatile solvent already present or newly added, can be used, for example, as an adhesive or to coat surfaces or to prepare solid structures by casting, possibly in a foamed state. The short fiber reinforcement can be incorporated with the composition before curing. Preferably a fiber-reinforced composition is prepared by passing essentially continuous fiber in contact with that resin composition. The resulting impregnated fibrous reinforcing agent can be used alone or in conjunction with other materials, for example, an additional amount of the same or different polymer or precursor of resin or mixture, to form a molded article. This technique is described in more detail in EP-A-56703, 102158 and 102159.
[00098] Another procedure comprises forming composition cured incompletely on film by, for example, compression molding, extrusion, melt-melting or belt-melting, laminating these films to fibrous reinforcing agent in the form of, for example, a non-mat relatively short fiber fabric, a woven cloth or essentially continuous fiber in conditions of sufficient temperature and pressure to cause the mixture to flow and impregnate the fibers and cure the resulting laminate.
[00099] Screens of impregnated fibrous reinforcing agent, especially as done by the procedure of one or more of EP-A 56703, 102158, 102159, can be laminated together by heat and pressure, for example, by molding with autoclave, vacuum or compression or by heated rollers, at a temperature above the curing temperature of the thermosetting resin or, if curing has already been carried out, above the glass transition temperature of the mixture, conveniently at least 180 ° C and normally up to 200 ° C and in a pressure in particular in excess of 1 bar, preferably in the range of 1-10 bar.
[000100] The resulting multi-fold laminate can be anisotropic in which the fibers are continuous and unidirectional, oriented essentially parallel to each other, or almost isotropic in each fold from which the fibers are oriented at an angle, conveniently 45 ° as in most laminates almost isotropic, but possibly, for example, 30 ° or 60 ° or 90 ° or intermediate, with the folds above and below. Intermediate orientations between anisotropic and quasi-isotropic, and combined laminates, can be used. Suitable laminates contain at least 4, preferably at least 8, folds. The number of folds depends on the application for the laminate, for example, the required strength, and laminates containing 32 or even more, for example, several hundred, of folds may be desirable. There may be aggregates, as mentioned above in interlaminate regions. Woven fabrics are an example of an almost isotropic or intermediate between anisotropic and almost isotropic.
[000101] The curable polymer composition is suitably adapted to be cured at a temperature lower than that of the material that constitutes the mold or tool in or in which it is intended to cure the resin composition becomes sensitive to heat in some way.
[000102] According to another aspect of the invention, a method is provided for making a thermosetting resin composition comprising disposing of the curable polymer composition as defined herein in an appropriate mold or tool, or equivalent state in which it is being formed, subjecting the composition to the desired elevated temperature at the appropriate pressure, for example, at atmospheric pressure and maintaining the temperature for a necessary period, as defined above.
[000103] According to another aspect of the invention, a composite is provided comprising pre-pregs as defined herein laminated together by heat and pressure, for example by autoclave, compression molding, or by heated rolls, at a temperature above temperature of curing the polymer composition.
[000104] In accordance with another aspect of the invention, a radar-absorbing composite is provided, capable of absorbing in one or more radar frequency bands in the range of 1-40 GHz, said radar-absorbing composite comprising one or more layers comprising the resin compositions defined herein or derivable from the curable polymer compositions defined herein. As defined here, radar frequency bands are selected from one or more of: L band (1-2 GHz), S band (2-4 GHz), C band (4-8 GHz), X band (8- 12 GHz), Ku band (12-18 GHz), K band (18-26.5 GHz) and Ka band (26.5-40 GHz). In one embodiment of the present invention, a radar-absorbing composite capable of absorbing radar in the X-band is provided.
[000105] As defined here, each layer can be derived from different curable polymer compositions or can have different fiber reinforcements or fillers. Each layer can be a single-fold laminate or a multi-fold laminate as defined here.
[000106] The radar absorbent composite can be a single absorbent layer 1, which is designed to have complex permissiveness and thickness adapted to reduce / minimize electromagnetic reflection in the selected frequency range (Figure 1), or it can be a multilayer absorber, as the layers of example 3, 4, 5 (Figure 2) comprising the resin compositions defined herein or derivable from the curable polymer compositions defined herein. The multilayer absorbent may, for example, include a layer 3 with low dielectric constant and a series of layers 4, 5, with increasing complex permissiveness values along the orthogonal absorber direction. Each absorbent layer may comprise thermosetting resin compositions defined herein and different nanocharge contents.
[000107] The compositions can be used neat, or as composite materials reinforced with fibers or fillers. The fibrous reinforcement preferably comprises fibers with a low dielectric constant such as swcrtzo qw xifto vkrq eqoq xifto “G”, “A”, “G-ET”, “E”, “F”, “T” and “U” Cu fibers can they may be continuous or they may, for example, be unidirectionally arranged fibers or woven, knitted or nonwoven knitted fabrics to form a pre-preg or they may be in the form of carpet, textiles or veil or the like. In an embodiment of the present invention, an Astroquartz fabric can be used.
[000108] The compositions may further comprise magnetic charges to provide improved absorption capacity or reduce the thickness of the radar absorbing material, said magnetic charges comprising magnetic metal microparticles such as carbonyl iron powder, ferrites and hexaferrites, nanocrystals and metallic magnetic nanoparticles.
[000109] According to another aspect of the present invention, a radar absorbing panel with reduced cross section is provided in one or more radar frequency bands in the range of 1-40 GHz, wherein said radar absorbing panel comprises the composite radar absorber defined herein and a highly conductive substrate 2, wherein that highly conductive substrate is preferably a structural carbon fiber reinforced composite. This structure is particularly suitable for manufacturing load-resistant or impact-resistant components with reduced radar cross-sectional signature control characteristics.
[000110] The present invention is applicable to the manufacture of composites by conventional pre-preg technology and also by resin infusion technology (as described, for example, in US-2004/0041128). Resin infusion is a generic term that covers processing techniques such as Resin Transfer Molding (RTM), Liquid Resin Infusion (LRI), Vacuum Assisted Resin Transfer Molding (VARTM), Resin Infusion with Flexible Tooling (RIFT ), Vacuum Assisted Resin Infusion (VARI), Resin Film Infusion (RFI), Controlled Atmospheric Pressure Resin Infusion (CAPRI), VAP (Vacuum Assisted Process) and Single Line Injection (SLI). The composites described herein particularly include composites formed through the use of resin-soluble thermoplastic veils in a resin infusion process as described in US-2006/0252334, the disclosure of which is incorporated herein by reference. In one embodiment, the composite is manufactured using the infusion resin in which a support structure comprising structural reinforcing fibers (dry) and the thermoplastic resin-soluble veil element is placed in a bag, mold or tool to provide a preform, a curable resin matrix composition is injected / infused directly into the fibers and combined structural reinforcement veil and then cured.
[000111] In accordance with another aspect of the invention, there is provided a molded thermoplastic thermoplastic or thermoplastic modified resin product comprising or derived from a composition, pre-preg or composite as defined above, particularly one that is obtained by a method according to defined above.
[000112] The compositions of the present invention find utility in any field where it is necessary to impart improved conductivity to a composite material. According to an embodiment of the present invention, the improvement in conductivity is an order of magnitude or more compared to conventional carbon fiber reinforced materials. Further improvements in conductivity can be transmitted to composite materials that do not include conductive reinforcement.
[000113] The compositions of the present invention find use in any field where it is necessary to adapt the permissiveness values in a selected frequency range or where it is necessary to transmit the ability to control signature to a composite component, or where it is necessary control the electromagnetic environment. For example, the large radar cross section and high speeds of the tip of the wind turbine blades can affect radar systems used for air traffic control, marine navigation and time monitoring. The reduction of the radar cross section of wind turbine blades is therefore an important requirement for, for example, wind farms in the vicinity of airports and offshore facilities. In addition, aircraft composite structures with reduced radar cross-section allow the control of electromagnetic wave propagation and reduce scattering phenomena and disturbances to signals generated by on-board antennas. In addition, the compositions of the invention also find use in composite structures for low observation vehicles. The present invention allows the preparation of composite materials and radar-absorbing structures that require the small radar cross section.
[000114] The present invention is applicable to the manufacture of components suitable for use in transport applications (including aerospace, aeronautical, nautical and land vehicles and including the automotive, rail and bus industries), including, for example, primary and secondary aircraft and space and ballistics structures. These structural components include composite wing structures. The present invention also finds use in building / construction applications and other commercial applications. As noted here, the compositions of the present invention are particularly suitable for the manufacture of load-resistant or impact-resistant structures.
[000115] The invention is now illustrated in a non-limited manner with reference to the following examples. EXAMPLES Measuring methods
[000116] The compositions of the invention can be characterized using the methods described below. Conductivity
[000117] Conductivity was determined for cured plates and composites using a Burster-Resistomat 2316 milli-ohmmeter that records resistance values as a ratio between applied voltage and current in a bridge method. Kelvin test probes were used to create a contact between the two sample surfaces. All measurements were performed in accordance with the 4-wire RT measurement method under standard humidity conditions.
[000118] The conductivity of the resin system was measured in cured resin coupons extracted from flat, smooth and uniform plates. Coupons with a thickness of approximately 3 mm square (lateral length = 40 mm ± 0.1 mm) were characterized. A commercial silver paste was used to create two electrodes on opposite surfaces of the coupon.
[000119] The conductivity in the z direction of the composite was measured in coupons extracted from defect-free panels prepared according to EN 2565 method B. Quasi-isotropic square samples of 2 mm thickness (lateral length = 40 mm ± 0.1 mm ) have been characterized.
[000120] The specimen surfaces of the composite were prepared by removing the resin-rich layer from the top to expose the carbon fibers underneath ensuring direct contact with the electrode. Then a commercial silver paste was used to create two electrodes on opposite surfaces of the coupon.
[000121] At least 5 samples per material and settlement were tested.
[000122] The DC electrical conductivity was calculated in [S / m] according to the following equation:
where: R is the measured resistance [Ohm]; l is the sample thickness [m]; S is the sample surface area [m2] Complex permittivity in the 8-12 GHz frequency range
[000123] The electromagnetic data were determined in cured resin composition. The liquid resins were cast and cured on standard Rectangular WR90 aluminum flanges with a thickness of 6 mm. The rectangular flanges containing the cured resin samples were then connected to an Anritsu 37347C network analyzer using an ATM waveguide WR90-120 A-666 and scanned in the frequency range 8 and 34 IJZo C rgtokuukxkfcfg ieff relative effective complex it is generally expressed go Vgtoqu fg uwcu rartgu tgcku g kocikpátkcu * ÍÓ g s. ” tgurgeVkxaogpVg + o Rcrtgu real and imaginary permissiveness in the frequency range of 8-12 GHz were calculated from measurements of the reflected signal, S11 and transmitted signal, S21 throughout the sample. Radar absorption in free space conditions
[000124] The measurement of the radar absorbing efficiency was performed on samples of 40 cm x 40 cm.quadrado. The test setup comprises an Anritsu 37347C network analyzer connected via a standard ATM WR90-120 A-666 rectangular waveguide to an ATM horn antenna 90-441-6. The antenna was positioned in front of the panel and used as an emitter and receiver of the EM signal reflected from the panel in free space conditions. The reflection coefficient was calculated at each frequency using the following formula:
is a ratio between the reflection coefficient dp (f) measured on the test panel and the reflection coefficient dm (f) measured on a metal reference plate.
[000125] The frequency range between 8 and 12 GHz has been explored. Morphology
[000126] Morphology was determined using High Resolution Field Emission Scanning Electron Microscopy (FEG-SEM). Before SEM analysis, the samples were conditioned in liquid nitrogen for 5 minutes and fractured to obtain a clear fracture surface. The samples were then coated with a gold film using a Quorum Technologies SC7620 coating sputter and examined using a LEO152 Gemini 1525 FEG-SEM. The observed morphologies analyzed were classified as homogeneous or as separated by phase. When separated by phase, the morphology was classified as:
[000127] macro phase separation: the heterogeneity of the resin system is observable through the eye. The resin is heterogeneous on the macro scale.
[000128] micro size morphology: the resin is homogeneous on a macro scale, but a closer investigation by SEM shows heterogeneity on the micron scale (particularly 1 to 100 μm).
[000129] sub-micrometric morphology: the resin is homogeneous on a macro scale. Closer investigation by SEM shows a secondary phase larger than 20 nm and up to 1 μm.
[000130] Micro and submicrometric size morphologies can be classified depending on their structure as well as:
[000131] cocontinuous: to describe a secondary phase that forms with the thermosetting matrix two completely intricate continuous phases (that is, infinite clusters). The system can also be described as interpenetrated polymer networks (IPN).
[000132] semicontinuous: to describe a secondary phase that forms an interrupted continuous network (that is, finite clusters) within a continuous thermosetting matrix. The system can also be described as semi-interpenetrated polymer networks (semi-IPN).
[000133] particulate: to describe a morphology in which the secondary phase is distributed in particles. The particles can be dispersed or aggregated forming a continuous network. A particulate morphology Vcodfio rqfg ugt fguetkVc eqoq woc guVtwVwtc fg "illicu-no-nicr" qpfg q oct corresponds to the continuous resin matrix and the islands to the particles. Particle size
[000134] The particle size distribution was measured using a Malvern Mastersizer 2000 operating in the range of 0.02μm to 2000μm. Glass transition temperature
[000135] The glass transition temperature is defined as the temperature where the sample shows a dramatic change in mechanical behavior and damping with increasing temperature when subjected to an oscillating displacement. The appearance of Tg is defined as the temperature at which the temperature intersection of the extrapolated tangents taken from the points of the storage module curve before and after the start of the glass transition event. The test was performed using TA Q800 in a single cantilever bending mode in the temperature range between about 50 ° C and 300 ° C, with a heating rate of 5 ± 0.2 ° C / min and the frequency of 1 Hz Three samples were tested and the Tg results were within ± 2 ° C of their mean. Fracture toughness
[000136] The fracture resistance of cured epoxies was measured using the compact tension method (CT), according to the ASTM D5045-99 standard. The CT sample had a nominal dimension of 41.2 x 39.6 x 5 mm. A sharp pre-crack was introduced for each CT sample by a shaving method to minimize the effects of residual stress and plastic deformation around the slit tip. A constant loading rate of 10 mm / min was adopted as recommended by ASTM D5045-99. An MTS 60484 strain gauge (max. 1.8 mm) was used to measure the displacement of the slit opening. Experimental I: Preparation of CNT-modified thermoplastic polymer
[000137] Three different concentrations of Nanocyl® NC7000 multi-wall carbon nanotubes (90% C purity; average diameter of 9.5nm, average length of 1.5μm; available from Nanocyl®, Belgium) were dispersed in a thermoplastic amine-terminated polyarylethersulfone (a PES: PEES copolymer of molecular weight 9000-12000 as defined here for component (A)) by means of a melt mixing process in a twin screw extruder. A pure sample of the same polyarylethersulfone was used as a control. High shear thread profiles comprising conventional mixing segments associated with chaotic mixing units to create the best balance between shear forces and pressure in the barrel optimizing dispersion levels without damaging the integrity of the nanocharge were used. The temperature profile and process conditions used are reported in Table 1.A. Table 1.A PES / MWCNT mixing dispersion equipment and corresponding process conditions

[000138] The resulting compounds were pelleted and then fused in cylindrical molds (diameter = 5cm; 2mm thick) using a Collin P300 P hot parallel plate press. Five samples per mixture were then tested as described above. The corresponding conductivity results are reported in Table 1.B. Table 1.B PES copolymer conductivity: PEES modified with MWCNT

[000139] The results demonstrate the efficiency of the dispersion method in dramatically improving the electrical conductivity of polyarylethersulfone at relatively low MWCNTs content. Specifically, an improvement of more than 15 orders of magnitude was achieved with 10% w / w nanocharge loads. II: Preparation of cured epoxy resins modified with CNT
[000140] Thus, the samples of Examples 1b and 1c were cryo-filled with Vcocpjq fg rcttíewnc ofifkq fg ognqu fg; 2 μo wucnfq wo ukuVgoc fg cryogenic Alpine grinding equipped with different rotary grinding media. Specifically, a number of passes using a prop, beaters, swing beaters and plate beaters were required to achieve the target particle size distribution. The CNT modified thermoplastic was dissolved in epoxy components (Araldite MY0510 and Araldite PY306; from Huntsman) of the formulation before the addition of the curing agent (Aradur 9664; Huntsman). The samples were then degassed before curing at 180 ° C for 3 hours, to produce Examples 2a and 2b. The control formulation was cured in the same way. In two additional experiments, similar formulations were prepared by dispersing the same MWCNTs in the same concentrations directly into epoxy resins (Araldite MY0510 and Araldite PY306; Huntsman) using a high-speed rotor mixer before dissolving the thermoplastic (PES copolymer: PEES ) and addition of the curing agent (Aradur 9664; Huntsman). The resulting formulations were then degassed and cured in the same way. The results of the DC electrical conductivity and permittivity at 10 IJz u «q tgncVcfqu pc Vcdgnc 4oC * go swg“ VR ”tgrtgugpVc“ Vgtoq ^ uVkeq ”+ o Table 2.A. Conductivity and permittivity values at 10 GHz of cured epoxy resin systems modified with CNT

[000141] The results demonstrate that the dispersion of the nanocharges in the epoxy resin is much more effective when the nanocharges are pretreated with the thermoplastic polymer compared to the samples in which the nanocharge is dispersed directly in the epoxy formulation. Example 2b produced the best results, improving the volume conductivity of the cured resin by more than 15 orders of magnitude compared to the unmodified sample. Figures 3 and 4, showing FEG-SEM micrographs of cured samples of the formulations of Example 2a and 2b confirm the excellent levels of dispersion achieved at both evaluated MWCNT concentrations.
[000142] Large nanotube clusters (40-92 μo + u «q. Rqt uwc xgz. Clearly visible for the cured formulations of Examples 2c and 2d containing the same nanocharge in the same concentration (Figures 5 and 6). Microscopic analysis still demonstrates the efficiency of the polyarylethersulfone dispersion method in achieving optimal nanocharge dispersion levels in the thermosetting resin composition without re-agglomeration during processing and curing.
[000143] Complex permissiveness was determined using the method described here. The results are shown in Figures 7a (real part of the permittivity (gó ++ g 9d * rcrtg kocikpátkc fc rgtokuukxkfcfg * góó ++ eqoq function of frequency).
[000144] The dispersion assisted by polyarylethersulfone of nanocarbons in the resin determines a substantial improvement in the real and imaginary parts. It was observed that the imaginary part of the complex permissiveness, which is directly associated with energy dissipation, increases much more rapidly depending on the charge content in the case of modified polyarylethersulfone / MWCNT systems compared to samples in which the nanocharge is dispersed directly in the epoxy formulation. These results can be explained on the basis of better dispersion levels achieved by the dispersion method disclosed in the invention. The higher values of the imaginary part of the complex permissiveness achieved in relatively smaller CNT contents can provide projectors with a powerful tool to reduce the thickness and, therefore, the weight of simple and multilayer microwave absorbers.
[000145] The impact of MWCNT / PES: PEES dispersions on the thermal properties of the cured resin composition was evaluated by Dynamic Mechanical Analysis (DMA).
[000146] The compositions of Example 2b and control 2 were degassed and cured at 180 ° C for 3h. 3 coupons per formulation were extracted from defect-free plates.
[000147] The use of MWCNT polyarylethersulfone dispersions does not substantially affect the glass transition temperature of the modified cured resin. Differences of less than 1 ° C were measured between unmodified formulations (control 2) and modified with CNT (Example 2b).
[000148] The impact of the MWCNT PES: PEES dispersions on the fracture resistance of the cured resin composition (KIc) was evaluated according to the Compact Tension (CT) method described here. The use of MWCNT polyarylethersulfone dispersions as in Example 2b does not substantially affect the fracture resistance values of the modified system. Differences of less than 5% were observed between the performance of control 2 and the modified MWCNT formulation of Example 2b. III: Preparation of fiber-reinforced composite samples
[000149] The resin system used in Example 2b was shot on the silicone release paper. The resulting resin film was impregnated with unidirectional carbon fibers of intermediate module, using a pilot scale UD prepregger that produced a pre-preg with a fiber weight per area of 196 g / m2 at 38% resin content.
[000150] Test panels (referred to as Example 3 here) were manufactured according to EN2565 by autoclaving curing 8 folds of the precook (quasi-isotropic settlement) for 3 hours at 180 ° C.
[000151] For comparison purposes, the Control 2 resin system was used to prepare identical unidirectional tapes and test panels (Control 3). The electrical conductivity of DC volume of the resulting composite samples was then measured according to a 4-wire volt-amperometric method. The results are shown in Table 3.A. Table 3.A Conductivity values of composites

[000152] A variety of mechanical tests were performed on the batches prepared according to Example 3 and Control 3 and the results are shown below in Table 3.B. Table 3.B Mechanical performance of carbon fiber reinforced composites modified with CNT

[000153] All tests and physical properties listed were determined at atmospheric pressure and room temperature (ie 20 ° C), unless stated differently here, or unless stated differently in referenced test methods and procedures. It can be seen that the dispersion of up to 3% of NC 7000 MWCNT using the approach revealed in the application does not have a noticeable impact on the mechanical properties of the structural composite material. IV: Preparation of the single-layer EM absorbent panel
[000154] Four different concentrations of multi-wall carbon nanotubes (98% C purity, average diameter of 15nm, available from Future Carbon®, Germany) were dispersed in an amine-terminated polyarylethersulfone thermoplastic (a PES: PEES copolymer of molecular weight 9000-12000 as defined here for component (A) through the melt mixing process according to the procedure described in example I. Table 4.A Polyarylethersulfone / MWCNT dispersions
The resultant compounds were pelleted and cryoomoido to a size of rctViewnc ofifkq fg ogpqu fg; 2 μo wucnfq wo ukuVgoc fg cryogenic Alpine code equipped with different rotary grinding media. The CNT-modified thermoplastic was dissolved in epoxy components (Araldite MY0510 and Araldite PY306; from Huntsman) from the formulations reported in Table 4B prior to the addition of the curing agent (Aradur 9664; Huntsman). Table 4.B Examples of Kurdish epoxy resin systems modified with CNT

[000155] The resulting compositions were degassed, cast on rectangular WR90 flanges and cured at 180 ° C for 3 hours.
[000156] The real parts (g ") g kocikpátkcu * gòò + fc rgtokuukxkfcfg gm frequency function for the formulations described in Examples 4e, 4f, 4g and 4h and control 2 are reported respectively in Figures 8a and 8b (the imaginary part of The experimental results demonstrate that a controlled increase in permittivity can be achieved by increasing the content of multi-wall carbon nanotubes in the frequency range of 8-12 GHz. The polymer dispersion method disclosed here provides the formulator with a powerful tool for modulating finely the nanocharge concentration and, later, the complex permissiveness of the modified resin system.
[000157] The resin system reported in Example 4c was filmed first on the silicone release paper and then used to impregnate an Astroquartz® III 8-Harness Satin fabric to produce a pre-preg with a fiber weight per area of 285 g / m2 at 38% w / w resin content. 12 folds were laminated and autoclaved at 180 ° C for 3 h under 6 atm pressure to produce a composite panel with a nominal thickness of 3.0 mm. A second, almost isotropic, fiber-reinforced composite panel [QI] 2s was manufactured by curing under the same conditions 8 folds of the unidirectional pre-preg described in Example 3 (Control 3), which was produced by impregnating intermediate module fibers with Control 2 resin. A single-layer radar absorbent panel was produced in accordance with the schematic in Figure 1 by the coalition of two panels using a 0.030 psf FM® 300-2M adhesive film (available from Cytec Engineered Materials) in an autoclave at 121 ° C for 90 minutes.
[000158] Figure 9 reports the loss of reflection of the composite panel measured in free space conditions as described here. The composite panel showed an absorption efficiency greater than 10 dB over the entire 8-12 GHz band, with a maximum of about 30 dB at 10 GHz. This result is generally considered satisfactory for the use of the present invention.
[000159] For comparison purposes, the Control 2 resin system was used to prepare otherwise identical Astroquartz pre-preg fabrics and test panels (Control 5 panel). Control Panel 5 was then bonded with an identical almost isotropic carbon fiber reinforced fiber panel using a 0.030 psf FM® 300-2M adhesive film as described above. The measured absorption efficiency was less than 2 dB in the measured frequency range (8-12 GHz).
[000160] The performance of the structure of the described invention cannot be achieved with a panel with the same thickness and structure (Control 6).
[000161] CNT-assisted polymer dispersion of CNTs in the resin matrix provides a flexible tool to precisely control the permissiveness values of modified resin compositions and pre-preg materials, allowing the design and manufacture of EM absorption panels from lightweight and structural. V: Comparative Example 5: dispersion of dry CNTs in epoxy resin precursors
[000162] The potential to enhance the electrical conductivity of an epoxy resin system was investigated using commercially available carbon nanotube products. The nanotubes were mixed in different concentrations with the epoxy component of the resin system and then dispersed using sonication or high-shear 3-neck milling. Comparative Examples 5a-5b:
[000163] For comparison purposes, control formulation 2 was modified using different polyethersulfone / CNT pre-dispersion contents of Example 1c, depending on the target nanocharge concentration. Comparative Examples 5c-5d:
[000164] Nanocyl® NC3100 (MWCNT; outside diameter 9.5nm; 95 +% purity) was dispersed in epoxy resins of the formulations reported using a Hielscher UP200S sonicator (operating at 24 kHZ; room temperature; 30 minutes). Comparative Example 5e-5f:
[000165] NanoAmor® MWCNTs (50-100nm inner diameter, 5-10nm outer diameter; 95% purity; available from Nanostructured & Amorphous Materials Inc, US) were dispersed in epoxy resins of the reported formulations using a Cole sonicator 750W Parmer (operating at 20kHz; amplitude = 37%; pulse = 3 seconds ON, 1 second OFF; room temperature; 30 minutes). Comparative Example 5g-5h:
[000166] NanoAmor® MWCNTs were dispersed in epoxy resins of the reported formulations using an Exakt triple roller mill in two passages. In the first pass, the initial gap was 15μm and the second gap was 5μm. In the second pass, the initial gap was 5 μm and a force applied to maintain the second gap in less than 1 μm.
[000167] For each of the Comparative Examples 5a to 5h, the curing agent was then added for the epoxy pre-dispersion at 100 ° C and the resulting system degassed and cured at 180 ° C for 3 hours. The conductivity of the cured samples was then measured according to the test described here. The conductivity of the cured control 2 sample was also less than 1 x 10-14 S / m. Table 5.A Conductivity values of cured resin samples modified with different commercial MWCNT types and content and according to different dispersion methods

[000168] Samples modified by high purity Nanocyl® NC3100 showed better conductivity than NanoAmor® MWCNT samples. Since the same dispersion method of nominal carbon purity (> 95%) was used, the difference in performance can be attributed to the different nanocharge aspect ratio and synthetic process. The sonicated NanoAmor® samples showed slightly better conductivity than the ground NanoAmor® samples, which may be the result of a lower level of dispersion or damage to the MWCNTs during the high shear grinding process. In general, however, an increase in conductivity between 11 and 12 orders of magnitude was observed for MWCNT concentrations above 0.2% w / w. The best conductivity achieved was about 1.5x10-2 S / m, which was observed for Nanocyl® 3100 MWCNTs of high purity (> 95%) at a concentration of 1% w / w dispersed in the epoxy component by sonication.
[000169] The conductivities reported in Table 5.A above for the examples according to the invention demonstrate the efficacy of the polyarylethersulfone thermoplastic polymer in dispersing the CNTs in the epoxy resin matrix in relation to Comparative Example 5b. In fact, much higher conductivity values, up to 1.4 x 10-1 S / m under CNT load 1% w / w, have been achieved with low purity nanocharges (90%). VI: Comparative Example 6: pre-dispersion of CNTs in epoxy resin precursors
[000170] Several pre-dispersions of carbon nanotubes in epoxy resin precursors are commercially available, and a series of experiments were carried out using the following products: (A): EpoCyl® NC E128-02 (NC7000 MWCNTs (90% purity) C) bisphenol-A epoxy master batch; Nanocyl®); (B): EpoCyl® NC E1MY-02 (NC7000 MWCNTs (90% C purity) TGMDA epoxy master batch (tetraglycidyl methylenedianiline); Nanocyl®); (C): Pellets Graphistrength CS1-25 (25% w / w MWCNT (90% C purity) master batch in bisphenol-A epoxy; Arkema®).
[000171] These dispersions were used to replace all or part of the epoxy component in the Control 2 resin system. For comparative example 6a, EpoCyl® NC E128-02 was used as a single epoxy component in the formulation to assess the full potential of the product . For comparative example 6b, the pre-dispersion was non-processable in isolation under any of the temperature and vacuum conditions attempted and was then used in combination (50:50 w / w) with the bisphenol-A epoxy dispersion of comparative example 6a . The curing agent was added for all epoxy mixtures at 100 ° C and the mixes vacuum degassed before curing at 180 ° C for 3 hours. The samples were then tested for conductivity according to the protocol described here. Table 6.A Conductivity values of modified cured resin systems using different commercial epoxy / MWCNT pre-dispersions

[000172] For comparative examples 6a and 6b, the best conductivity values obtained were 6x10-6 S / m and 3x10-11 S / m, respectively, and therefore significantly lower than the compositions of the present invention.
[000173] For comparative examples 6c.1, 6c.2, 6c.3, Arkema Graphistrength® CS1-25 epoxy pre-dispersion was used in different concentrations to replace part of the difunctional epoxy component in the resin system of control 2, depending on the target MWCNT content. A good conductivity improvement was measured with a maximum of 0.3 S / m, being observed for a sample with a final concentration of 3% w / w CNTs in the epoxy resin.
[000174] Figure 10 shows a FEG-SEM micrograph of a cured sample of the formulation of Example 6c.2. Although a discontinuous percolation network is observable, large clusters of MWCNT in the range 20-62 μo u «q enctcogpVg xkuixgku. fgoqpuVtcpfq c kpgfíekêpekc of the master batch CS1-25 epoxy / MWCNT in properly dispersing the nanocharge in the epoxy resin composition.
[000175] The results show that the compositions of the present invention are functional for achieving conductivity values that are much better than those of the prior art, without the need to use relatively expensive commercial master batches. The revealed technology offers particular advantages for formulators due to the high concentration of MWCNT. It also offers an advantage of the process, with the possibility to efficiently control the introduction of MWCNT in the resin formulation using conventional mixing equipment and during standard pre-preg manufacturing processes.
[000176] VII: Comparative Example 7: pre-dispersions of CNTs in a conventional thermoplastic polymer to release CNTs in the epoxy resin
[000177] Graphistrength® C M13-30 (Arkema, France) is a commercially available master batch with high loads (approximately 30% w / w) of MWCNTs in a thermoplastic terpolymer (styrene / butadiene / methylmethacrylate) designed for applications of electrostatic discharge (ESD) protection. A series of experiments was carried out using different concentrations of the master batch C M13-30 dissolved in epoxy components of the resin systems reported in the Table while being sonicated (Cole Parmer sonicator operated as above, except for a temperature of 130 ° C). The concentration of MWCNTs in relation to the composition of the total resin system was in the range of 0.5 to 3% w / w.
[000178] The curing agent was then added and the resulting system degassed and cured at 180 ° C for 3 hours. The samples were then tested for conductivity according to the protocol described here. Table 7.A Conductivity values of modified control curing resin 2 systems with different contents of Graphistrength® CM13 30.

[000179] The percolation threshold was reached only at MWCNT concentrations greater than about 1.2% w / w. The highest conductivity achieved was only about 2 x 10-1 S / m with loads of CNT 3% w / w. The relatively small increase in conductivity may be a result of no interaction or limited interaction between the nanocharge and the methacrylate polymer and the insufficient levels of dispersion achievable due to the suboptimal compatibility of the master batch in the resin formulation. Figure 11 shows a FEG-SEM micrograph of a cured sample of the formulation of Example 8a. The cured system has a particulate morphology with micrometric thermoplastic domains distributed in the resin matrix. Clusters of MWCNT with a size in the range of 3-7 μo u «q enctcogpVg xkuixgku eqoq tguwnvcfq fc fkurgtu« q nkokVcfc g dckzc distribution of the nanocharge in the resin matrix.
[000180] The conductivity values reported in Table 2 for the examples according to the invention demonstrate the effectiveness of the polyarylethersulfone thermoplastic polymer in dispersing the CNTs in the epoxy resin matrix in relation to Comparative Example 7. VIII: Comparative Example 8: dispersing CNTs in thermoplastic polymers to release CNTs in the epoxy resin
[000181] A series of experiments were carried out to compare the polyarylethersulfone thermoplastic polymer used in examples 1 to 5 with commercially available thermoplastic curing agents for the ability to increase the conductivity of an epoxy resin system. The thermoplastics (TP) used were polyimide (Matrimid® 9725; Huntsman) and polyetherimide (Ultem® 1000; GE Plastics). A concentration of 10% w / w of CNTs in the thermoplastic was used in all experiments. Nanocyl NC7000 industrial MWCNTs (90% C purity) were dispersed in thermoplastic polymers using a Prism extruder equipped with a 24mm double-threaded coil with a LD ratio of 40 to 1. The temperature profile reported in Table 8.B was developed to guarantee ideal shear / pressure values along the barrel and ideal nanocharge dispersion levels in the thermoplastic matrix.


[000182] The CNT modified thermoplastic was combined with the epoxy components of the resin system as described for Examples 2 above prior to the addition of the curing agent. The samples were then degassed before curing at 180 ° C for 3 hours. Conductivity was measured according to the method described here. The results for each cured epoxy resin system modified with CNT are shown in Table 8.C below. Table 8.C Conductivity values of cured epoxy resin systems modified with CNT

[000183] The results demonstrate the greater conductivity of the samples in which polyarylethersulfone was used to disperse the CNTs in the epoxy resin in relation to the commercially available polyetherimide and polyimide thermoplastic hardening agents. IX: Comparative Example 9: dispersing CNTs in thermoplastic polymers to release CNTs in the epoxy resin
[000184] A series of experiments were carried out to compare the amine-terminated polyarylethersulfone thermoplastic polymer used in Examples 1 to 5 with 100% non-reactive chlorine-terminated polyethersulfone curing agents for the ability to increase the conductivity of an epoxy resin system. The thermoplastic was synthesized according to the procedure described in WO9943731A2 using a moderate excess of activated aromatic halide to produce a polymer with 100% halogenated terminal groups.
[000185] Two different concentrations of Nanocyl® NC7000 multi-wall carbon nanotubes (90% C purity; 9.5 nm medium diameter, 1.5 µm medium length; available from Nanocyl®, Belgium) were dispersed in the thermoplastic of chlorine-terminated polyethersulfone (a PES polymer of 15-18 K molecular weight) through a melt mixing process as described in Example 1. The temperature profile and process conditions used are reported in Table 9.A. Table 9.A PES / MWCNT mixing dispersion equipment and


[000186] The CNT modified thermoplastic was combined with the epoxy components of the resin system as described for Examples 2 above prior to the addition of the curing agent. The samples were then degassed before curing at 180 ° C for 3 hours. Conductivity was measured according to the method described here. The results for each cured epoxy resin system modified with CNT are shown in Table 9.C below.

[000187] The results demonstrate the greater conductivity of the samples in which the reactive polyarylethersulfone described in the patent claims was used to disperse the CNTs in the epoxy resin in relation to polyethersulfone terminated with non-reactive chlorine. X: Preparation of the dispersion of Polyethersulfone / CNT through the in situ polymerization pathway
[000188] 1 g of single-walled carbon nanotubes (Thomas Swan; UK) was added to a container containing 100 ml of sulfolane and dispersed using a sonicator. The sonicator's micro-tip was immersed approximately 1 cm in the suspension and set to an amplitude of 37%. The probe was pulsed for 3 seconds and turned off for 1 second. This was done for 4 hours; therefore the total pulse in time was 3 hours. This material was used as half of the 200ml of solvent for the synthesis of the PES: PEES copolymer using the synthetic route described in example 1.1 of WO9943731A2, incorporated herein. 65,000g of dichlorodiphenylsulfone, 21,741 g of bisphenol-S, 14,348 g of hydroquinone and 2,002 g of meta aminophenol were added to a 500ml reaction vessel. The 100ml of CNT / sulfolane pre-dispersion was at this stage along with another 100ml of sulfolane. The monomers were stirred overnight under nitrogen at room temperature. 32.203g of potassium carbonate were added to the mixture along with another 50ml of sulfolane. The container was heated to 180 ° C and maintained for 30 minutes, then heated to 210 ° C and maintained for 1 hour and finally heated to 230 ° C and maintained for 4 hours. The resulting black viscous liquid polymer was precipitated in water and washed with several batches of hot water. The washing phases finally yielded a gray powder. XI: Preparation of polyethersulfone / CNT fibers by combining the in situ polymerization / melt extrusion route
[000189] The resulting polyarylethersulfone / CNT dispersion was fed into a Prism extruder equipped with a 24mm corotation double screw with an LD ratio of 40 to 1. The same temperature profile reported in Table 1 Example 1a / b was used to ensure ideal shear / pressure values along the barrel and ideal nanocharge dispersion levels in the thermoplastic matrix. Fibers of approximately 100-200 microns were produced.

权利要求:
Claims (20)
[0001]
1. Process for the production of a composition comprising one or more conductive nanocharges, one or more polyarylethersulfone thermoplastic polymers (A), one or more uncured thermosetting resin precursors (P) and, optionally, one or more curing agents for the same, characterized by the fact that said process comprises mixing or dispersing a first composition comprising one or more conductive nanocharges and one or more polyarylethersulfone thermoplastic polymers (A) with or in one or more uncured thermosetting resin precursors (P) and optionally one or more curing agents for them.
[0002]
2. Process according to claim 1, characterized by the fact that said nanocharge is coated or wrapped with one or more macromolecules of the thermoplastic polymer (A).
[0003]
3. Process, according to claim 1 or 2, characterized by the fact that said first composition comprises said conductive nanocharge (CNF) in an amount that the mass fraction W (CNF) is from 1% to 20%, in that W (CNF) is calculated as: W (CNF) = M (CNF) / (M (A) + M (CNF)) where M (CNF) is the mass of the conductive nanocharge in said first composition, and M (A ) is the mass of the thermoplastic polymer (A) in said first composition, and in which the amount of thermoplastic polymer (A) combined with the resin precursor is such that the mass fraction W (A), calculated as W (A) = M (A) / M, where M (A) is the mass of the thermoplastic polymer (A) present in the cured thermoset resin composition having the mass M is 0.5% to 40%.
[0004]
4. Process, according to claim 1, characterized by the fact that said first composition is in micronized particulate form, and in a mode in which the micronized particulate has an average particle size in the range of 10 to 150 μm.
[0005]
Process according to any one of claims 1 to 4, characterized in that said polyarylethersulfone thermoplastic polymer (A) comprises repeating units linked by ether, optionally also comprising repeating units linked by thioether, the units being selected from : - [ArSO2Ar] n- and optionally from: - [Ar] a- where: Ar is phenylene; n = 1 to 2 and can be fractional; a = 1 to 3 and can be fractional and when it exceeds 1, said phenylene groups are linearly linked through a single chemical bond or a divalent group other than -SO2- (preferably where the divalent group is a -C group (R9 ) 2- where each R9 can be the same or different and selected from H and C1-8 alkyl (methyl)), or are fused together, provided that the repeating unit - [ArSO2Ar] n- is always present in the polyarylethersulfone in a proportion that on average at least two of the said units - [ArSO2Ar] n- are in sequence in each polymer chain present, and in which the polyarylethersulfone has one or more reactive pendant and / or end groups.
[0006]
6. Process according to any one of claims 1 to 5, characterized by the fact that the repetition units in said polyarylethersulfones are: (I): -X-Ar-SO2-Ar-X-Ar-SO2-Ar- and (II): -X- (Ar) aX-Ar-SO2-Ar- where: X is O or S and can be different from unit to unit and in one mode it is O; and the unit I: II ratio is preferably in the range of 10:90 to 80:20.
[0007]
7. Process according to claim 9, characterized by the fact that polyarylethersulfone contains one or more reactive groups pending and / or terminals selected from groups that provide active hydrogen and groups that provide other cross-linking activity, in which more than a relatively smaller proportion of terminal groups in the polymer are halo groups; optionally in which said pending and / or reactive end (s) group (s) is / are selected from groups providing active hydrogen selected from OH, NH2, NHRb and -SH, where Rb is a group hydrocarbon containing up to eight carbon atoms and in an OH and NH2 modality.
[0008]
8. Process according to any one of claims 1 to 7, characterized by the fact that the carbon-based nanocharge is selected from carbon nanotubes, and in a multi-walled carbon nanotube modality.
[0009]
Process according to any one of claims 1 to 8, characterized in that it comprises mixing or dispersing said first composition with or in a second composition comprising one or more uncured thermosetting resin precursors (P) and further comprising one or more polyarylethersulfones and one or more conductive nanocharges and, optionally, one or more curing agents therefor, wherein said polyarylethersulfone (s) in said second composition may be the same or different ( (s) of the polyarylethersulfone (s) in the first composition and said conductive nanocharge (s) in the second composition can be the same or different from the conductive nanocharge (s) in the first composition.
[0010]
Process according to any one of claims 1 to 9, characterized by the fact that said conductive nanocharge (s) dispersed in, or coated or surrounded with, said polymer (s) ( s) thermoplastic (s) is / are dissolved in said thermosetting resin precursor formulation.
[0011]
Process according to any one of claims 1 to 10, characterized by the fact that one or more curing agents is / are present, in which the curing agent (s) is / are added after mixing said one or more uncured (P) thermosetting resin precursors, one or more conductive polyarylethersulfones and nanocharge (s).
[0012]
12. Process according to any one of claims 1 to 11, characterized in that it further comprises the stage of curing the composition.
[0013]
Process according to any one of claims 1 to 12, characterized in that at least a portion of said conductive nanocharge (s) is dispersed, or coated or wrapped with, said (s) thermoplastic polymer (s) (A) before mixing or contacting said thermosetting resin precursor (s) (P).
[0014]
Process according to any one of claims 1 to 13, characterized by the fact that it comprises the polymerization of said thermoplastic polymer (s) (A) in which said conductive nanocharge is present during the synthesis of said thermoplastic polymer; and in a modality in which a reaction mixture is contacted, optionally in the presence of a catalyst, with the nanocharge or before the beginning of said polymerization reaction or during the polymerization reaction; and in another embodiment, in which said process comprises the steps of (i) preparing a suspension of said conductive nanocharge (s) in an inert solvent; and (ii) prepare a reaction mixture from the nanocharge suspension and optional catalyst by adding the monomeric reagents and conducting the polymerization reaction.
[0015]
15. Process according to any one of claims 1 to 13, characterized by the fact that it comprises mixing said nanocharge and fused thermoplastic polymer (A) in a single or double screw extruder using chaotic and high shear mixing profiles to produce a first composition comprising at least a portion of said conductive nanocharge (s) is dispersed, or coated or enveloped with, said thermoplastic polymer (s) (A).
[0016]
16. Process according to any one of claims 1 to 15, characterized in that said first composition is in the form of a pelleted product, micronized particulate product, continuous or cut fiber, fibrous material or woven and non-woven fabric.
[0017]
17. Process according to any one of claims 1 to 17, characterized by the fact that it comprises the micronization step of said first composition so that said first composition is in micronized particulate form before mixing or contacting said (s) precursor (s) of thermosetting resin (P).
[0018]
18. Process according to any one of claims 1 to 17, characterized in that the resin precursor (s) is / are selected (s) from mono- or polyglycidyl derivatives from one or more of the group of compounds consisting of aromatic diamines, aromatic monoprimary amines, aminophenols, polyhydric phenols, polyhydric alcohols, polycarboxylic acids and the like or a mixture thereof, and in a modality in which the precursor (s) of epoxy resin is / are selected (s) from: (i) glycidyl ethers of bisphenol A, bisphenol F, dihydroxydiphenyl sulfone, dihydroxybenzophenone and dihydroxy diphenyl; (ii) epoxy resins based on Novolacs; and (iii) glycidyl functional reaction products of m- or p-aminophenol, m- or p-phenylene diamine, 2,4-, 2,6- or 3,4-toluylene diamine, 3,3'- or 4, 4'-diaminodiphenyl methane, wherein the epoxy resin precursor has at least two epoxy groups per molecule.
[0019]
19. Composition, characterized by the fact that it comprises conductive nanocharges, a polyarylethersulfone thermoplastic polymer (A), one or more uncured thermosetting resin precursors (P) and one or more curing agents for the same, in which said nanocharge is coated or enveloped with one or more macromolecules of the thermoplastic polymer (A), and where the polyarylethersulfone contains one or more reactive pendant and / or end groups selected from the groups providing active hydrogen and groups providing other cross-linking activity, where no more that a relatively small proportion of end groups in the polymer are halo groups and in which the thermosetting resin precursor (P) is selected from epoxy resin precursors having at least epoxide group per molecule.
[0020]
20. Composite, characterized by the fact that it comprises the composition as defined in claim 19 and reinforcement fibers, wherein said fibers are present in a concentration of 5 to 70% by weight.

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US10236092B2|2019-03-19|

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JP2015508437A|2015-03-19|

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TW201335281A|2013-09-01|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-16| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-11-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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GB1122296.5|2011-12-23|

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GBGB1122296.5A|GB201122296D0|2011-12-23|2011-12-23|Composite materials|

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PCT/US2012/070472|WO2013141916A2|2011-12-23|2012-12-19|Composite materials comprising conductive nano-fillers|

---