Indian Patents. 252126:"PREFORMED COMPOSITIONS IN SHAPED FORM COMPRISING POLYMER BLENDS"

Title of Invention	"PREFORMED COMPOSITIONS IN SHAPED FORM COMPRISING POLYMER BLENDS"
Abstract	Preformed compositions in shaped form comprising polymer blends, and the use of these preformed compositions in shaped form to seal apertures are disclosed, the preformed compositions being electrically conductive and capable of shielding EMT/RFI radiation, and the said polymer blend includes a polysulfide component and a polythioether component.

Full Text	PREFORMED COMPOSITIONS IN SHAPED FORM COMPRISING POLYMER BLENDS FIELD OF THE INVENTION [001] The present Invention relates to preformed compositions in shaped form and the use of preformed compositions for sealing apertures. BACKGROUND OF THE INVENTION [002] Electromagnetic interference can be defined as undesired conducted or radiated electrical disturbances from an electrical or electronic source, including transients, that can interfere with the operation of other electrical or electronic apparatus. Such disturbances can occur at frequencies throughout the electromagnetic spectrum. Radio frequency interference ("RFI") is often used interchangeably with electromagnetic interference ("EMI"), although RFI more property refers to the radio frequency portion of the electromagnetic spectrum usually defined as 10 kilohertz (KHz) to 100 gigahertz (GHz). [003] Electronic equipment is typically enclosed in a housing. The housing not only serves as a physical barrier to protect the equipment from the environment, but also can serve to shield EMI/RFJ radiation. Enclosures having the ability to absorb and/or reflect EMI/RFI energy may be employed to confine the EMI/RFI energy within the source device, and to Insulate the device or other external devices from other EMI/RFI sources. To maintain accessibility to the internal components, most enclosures are provided with openable or removable accesses such as doors, hatches, panels, or covers. Gaps typically exist between the accesses and the corresponding mating surfaces that reduce the efficiency of the electromagnetic shielding by presenting openings through which radiant energy may be emitted. Such gaps also present discontinuities in the surface and ground conductivity of the housing, and in some cases may generate a secondary source of EMI/RFI radiation by functioning as a slot antenna. [004] For filing gaps between the mating surfaces of the housing and removable accesses, gaskets and other seals are used to maintain electrical continuity across the structure, and to exclude environmental degradants such as particulates, moisture, and corrosive species. Such seals are bonded or mechanically attached to one or both of the mating surfaces and function to establish a continuous conductive path by conforming to surface irregularities under an applied pressure, [005] Conventional processes for manufacturing EMI/RFI shielding gaskets include extrusion, molding, and die-cutting. Molding involves the compression or injection molding of an uncured or thermoplastic resin into a certain configuration. Die-cutting involves the forming of a gasket from a cured polymeric material, which is cut or stamped into a certain configuration using a die. Form-in-place (TIP") processes are also used for forming EMI/RFI shielding gaskets wherein the process involves the application of a bead of a viscous, curable, electrically-conductive composition in a fluent state to a surface that is subsequently cured-in-place by the application of Heat, atmospheric moisture, or ultraviolet radiation to form an electrically-conductive, EMI/RFI shielding gasket. [006] Electrical conductivity and EMI/RFI shielding effectiveness is typically Imparted to polymeric gaskets by incorporating conductive materials within the polymer matrix. The conductive elements can include metal or metalplated particles, fabrics, meshes, and fibers. The metal can be in the form of, for example, filaments, particles, flakes, or spheres. Examples of metals include copper, nickel, silver, aluminum, tin, and steel. Other conductive materials that are used to impart EMI/RFI shielding effectiveness to polymer compositions include conductive particles or fibers comprising carbon or graphite. Conductive polymers such as polythiophenes, polypyrroles, polyaniline, poly(pphenylene) vinylene, polyphenylene sulffde, polyphenylene, and polyacetylene may also be used. [007] In addition to shielding EMI/RFI radiation, in certain applications it is also desirable that the seal be transparent to incident broad spectrum radiation used for detection, location, or recognition purposes. For example, microwave radiation from 5-18 GHz, 35 GHz, 94 GHz. 140 GHz and 220 GHz has useful military significance. Electromagnetic radiation incident on a surface will be partly reflected and partly absorbed by the material and the sum of these effects determines the shielding effectiveness. The shielding effectiveness depends on several factors including the frequency of the electromagnetic radiation, the conductivity of the shielding material, the thickness and permeability of the shielding material, and the distance between the radiating source and the EMI/RFI shield. At high frequencies, above about 10 GHz, shielding effectiveness is primarily determined by the ability of the shielding material to absorb the incident radiation. Ferromagnetic particles with high permeability such as iron, carbonyl iron, cobalt metal alloys, and nickel metal alloys are used as radar absorbing materials. [008] In addition to providing continuous electrical conductivity and EMI/RFI shielding effectiveness, in certain applications H is desirable that gasket or seals to surfaces exposed to the environment, such as in aviation and aerospace vehicles, not lead to corrosion of the metal surfaces. When dissimilar metal and/or conductive composite materials are joined in the presence of an electrolyte, a galvanic potential is established at the interface between the dissimilar conductors. When the interfacial seal is exposed to the environment, particularly under severe environmental conditions such as salt fog or salt fog containing a high concentration of SO2, corrosion of the least noble of the conductive surfaces will occur. Corrosion may lead to a degradation in the EMI/RFI shielding effectiveness of the seal. Mechanisms other than galvanic potentials, e.g. crevice corrosion, may also compromise the electrical and mechanical integrity of the enclosure. [009] Polysulfide polymers are known in the art. The production of polysulfide polymers is characterized by Fettes and Jorzak, Industrial Engineering Chemistry, November, 1950, on pages 2,217 to 2,223. The commercial use of polysulfide polymers in the manufacture of sealants for aerospace applications has long been known and commercially used. Polysulflde sealants have been used to seal aircraft exterior fuselage because of the high tensile strength, high tear strength, thermal resistance, and resistance to high ultraviolet light. Polysulfide sealants have been used to seal aircraft fuel tanks because of the resistance to fuel and adhesion upon exposure to fuel. [010] Polysulfide sealants are generally applied by extrusion using a gun. Extruding a sealant to seal apertures in airframe such as those associated with access doors or panels can require a significant amount of effort. The interior perimeter of the access door opening is masked and the exterior perimeter of the access door is coated with a release agent to avoid sealing an access door shut. The sealant is extruded and the access door is put In place and clamped down to force the excess sealant around the access door. The sea/ant is allowed to cure and the excess sealant is trimmed away. This process is time intensive and can add significant labor demands for servicing aircraft with many access doors. Some aircraft can have as many as a hundred or more access doors that are used to cover sensitive electronic equipment or fittings that must be periodically accessed. [011] Accordingly, it is desirable to provide compositions and methods for sealing access doors, for example those in an airfrarne of an aviation or aerospace vehicle, that are not as labor and time intensive as the conventional extrusion method for sealing the access doors. It is also desirable to provide such compositions and methods that further provide effective EMI/RFI shielding and cause minimal corrosion to conductive surfaces. SUMMARY OF THE INVENTION [012] The present invention is directed to preformed compositions in shaped form, comprising a polymer blend that comprises at least one polysulfide component and at least one polythioether component. [013] The present invention is further directed to methods for sealing an aperture comprising: (a) covering the aperture with the preformed composition of the present invention in shaped form; and (b) curing the composition so as to seal the aperture. DETAILED DESCRIPTION OF THE INVENTION [014] The present invention is directed to a preformed composition in shaped form comprising a polymer blend comprising at least one polysulfide component and at least one polythioether component. The term "preformed11 refers to a composition that can be made into a particular shape for ease of packaging, storage, and/or application. A composition that is preformed can be reshaped into any shape, either intentionally, or as a result of shipping and/or handling. The term "shaped form" refers to a configuration such that the thickness of the preformed composition is substantially less than the lateral dimension and includes but is not limited to tapes, sheets and cut-out or gasket forms. The "shaped form" can be in the form of a tape meaning a narrow shape, strip, or band that can be stored as rolls, coils, or strips. The "shaped form" can also be die-cut to the dimensions of the aperture to be sealed. [015] "Sealant" and like terms refer to compositions that have the ability to resist atmospheric conditions such as moisture and/or temperature and/or at least partially block tne transmission of materials such as water, fuel, and/or other liquids and gasses. Sealants often have adhesive properties, as well. "Aperture" refers to a hole, gap, slit or other opening. The term "elongated aperture" refers to such an opening in which the length is at least three-times the width. "Shielding" and like terms refer to the ability to divert, route, and/or reflect incident electromagnetic energy. Shielding effectiveness represents the ratio of the electromagnetic energy passing through a shield to the electromagnetic energy striking the shield. [016] The polymer blend of the present invention comprises at least one polysulfide component and at least one polythioether component. The "polysulfide component" of the present invention comprises a polysulfide polymer that contains multiple sulfur-sulfur linkages, i.e., —[S—S]—, in the polymer backbone and/or in the terminal or pendant positions on the polymer chain. Typically, the polysulfide polymers in the present invention will have two or more sulfur-sulfur linkages. Suitable polysulfides are commercially available from Akzo Nobel under the name THIOPLAST. THIOPLAST products are available in a wide range of molecular weights ranging, for example, from less than 1100 to over 8000, with molecular weight being the average molecular weight in grams per mole. Particularly suitable as a number average molecular weight of 1000 to 4000. The crosslink density of these products also varies, depending on the amount of crosslinking agent used. The "—SH" content, i.e. the mercaptan content, of these products can also vary. The mercaptan content and molecular weight of the polysulfide can affect the cure speed of the blend, with cure speed increasing with molecular weight. [017] In some embodiments, it is desired to use a combination of pojysulfides to achieve the desired molecular weight and/or crosslink density in the polymer blend. Different molecular weights and/or crosslink densities can contribute different characteristics to the blend and compositions incorporating the blend. For example, blends wherein the polysulfide component comprises more than one polysulfide polymer and one of the polysulfide polymers has a molecular weight of approximately 1000 have desirable non-crystallization properties. [018] The second component in the polymer blend of the present invention is a polythioether. The "polythioether component" of the present invention is a polymer comprising at least one polythioether linkage, i.e., -[—CHa—GHz—S—CHz—CHr-]-. Typical polythioethers have from 8 to 200 of these linkages. Polythioethers suitable for use in the present invention indude those described in U.S. Patent No. 6,372,849. Suitable polythioethers typically have a number average molecular weight of 1000 to 10,000, such as 2,000 to 5,000, or 3,000 to 4,000. In some embodiments, the polythioether component will be terminated with non-reactive groups, such as alkyl, and in other embodiments will contain reactive groups in the terminal or pendant positions. Typical reactive groups are thiol, hydroxyl, amino, vinyl and epoxy. For a polythioether component that contains reactive functional groups, the average functionality typically ranges from 2.05 to 3.0, such as from 2.1 to 2.6. A specific average functionality can be achieved by suitable selection of reactive ingredients. Examples of suitable polyth/oethers are available from PRC-Desoto international, Inc., under the trademark PERMAPOL, such as PERMAPOL P- 3.1 E or PERMAPOL P-3. As with the polysulfide component, combinations of polythioethers can be used to prepare the polythroether component according to the present invention. [019] The polymer blends of the present invention can be prepared according to any standard means known in the art, such as by mixing the polysulfide component and polythioether component and blending in a standard mixer such as a cowls mixer or planetary mixer. The ratio of polysulfide component to polythioether component in the blend can range from 10:90 to 90:10. A 50:50 ratio is particularly suitable for some embodiments. The molecular weight of the present polymer blend is typically from 1000 to 8000, such as 3500 to 4500, as measured theoretically or using GPC. The Tg of the polymer blend is typically ~70°C or lower, such as -60°C or lower. The viscosity of the blend will typically be lower than the viscosity of a polysulfide having a comparable molecular weight; this contributes to the ease of handling of the present compositions and may minimize if not eliminate the need for solvents. 1020] The polymer blend in the present compositions typically comprises 10 to 50 weight percent, such as 20 to 30 weight percent, with weight percent based on the weight of the total preformed composition. [021] In certain embodiments, the preformed composition of the present invention further comprises a suitable curing agent. The term "curing agent" refers to any material that can be added to accelerate the curing or gelling of the polymer blend. In some embodiments, the curing agent is reactive at 10°C to 80°C. The term "reactive" means capable of chemical reaction and includes any level of reaction from partial to complete reaction of a reactant. in certain embodiments, a curing agent is reactive when it provides for cross-linking or gelling of a sulfur-containing polymer. "Cure" refers to the point at which the composition achieves a cure hardness of 30 Durometer "A" as measured according to ASTM D2240. [022] In certain embodiments, the preformed composition comprises a curing agent that contains oxidizing agents that oxidize terminal mercaptan groups in the polymer blend. Useful curing agents include lead dioxide, manganese dioxide, calcium dioxide, sodium perborate monohydrate, calcium peroxide, zinc peroxide, dichromate and epoxy. Other suitable curing agents may contain reactive functional groups that are reactive with the functional groups in the polymer blend. Examples include but are not limited to polythiols, such as polythioethers; polyisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, and mixtures and isocyanurate derivatives thereof; and polyepoxides. Examples of polyepoxides include hydantoin diepoxide, Bisphenol-A epoxides, Bisphenol-F epoxides, Novolac-type epoxides, aliphatic polyepoxides, and epoxidized unsaturated and phenolic resins. The term "polyepoxide" refers to a material having a 1,2-epoxy equivalent greater than one and includes monomers, oligomers, and polymers. Cure accelerators or retardants can also be used, such as a dimethylene/thiuram/polysulfide mixture cure accelerator or a stearic acid cure retarder, which will retard the rate of cure thereby extending the "pot life" of the composition. To control the properties-of the composition, one or more materials capable of at least partially removing moisture from the composition, such as molecular sieve powder. [023] The preformed compositions of the present invention can also comprise one or more additives. "Additives" refer to non-reactive components in the preformed composition that provides a desired property. Examples of additives include but are not limited to fillers, adhesion promoters, and plasticizers. Fillers useful in the present compositions, especially for aerospace applications, include those commonly used in the art, such as carbon black, calcium carbonate (CaCO3), silica, nylon and the like. Potting compound fillers illustratively include high band gap materials such as zinc sulfide and inorganic barium compounds. In one embodiment, the compositions include about 10 to about 70 weight percent of the selected filler or combination of fillers, such as about 10 to 50 weight percent based upon the total weight of the composition. In one embodiment, a combination of mica and polyamide are used as the filler component. [024] Mica is a silicate characterized by basal cleavage that imparts flexibility to laminas. Micas include natural muscovite, phlogopite, and biotite, as well as synthetic fluorophlogopite and barium disilicic. Preparation of synthetic micas is described in Encyclopedia of Chemical Technology, Vol. 13, pp. 398- 424, John Wiley & Sons (1967). Mica provides flexibility and pliability to the preformed composition and reduces the tack, Polyamide powder provides viscosity and reduces the tack of the preformed composition. Polyamide resins can be produced by the condensation reaction of dimerized fatty acids, such as dimerized linoleic acid, with lower aliphatic polyamines, such as for example, ethylene diamine or diethylene triamine, so that the final product has multiple amide groups in the resin backbone. A process for the manufacture of polyamide resins is disclosed in U,S. Patent No. 2,450,940. Polyamide resins . suitable for the preformed composition are solid at use temperature and typically have a number average molecular weight of at least 10,000 Daltons. [025] In certain embodiments, mica and polyamide together form 10 percent by weight to 50 percent by weight of the total weight of the preformed composition with substantially equal amounts of mica and polyamide. "Substantially equal" means that the amount of mica and the amount of polyamide are present in an amount of less than 5 percent of each other. The amount of mica can range from 5 percent by weight to 25 percent by weight and the amount of polyamide from 5 percent by weight to 25 percent by weight. In one embodiment, the amount of mica ranges from 10 percent by weight to 20 percent by weight and the amount of polyamide ranges from 10 percent by weight to 20 percent by weight of the total weight of the preformed composition. [026] One or more adhesion promoters can also be used. Suitable adhesion promoters include phenolics such as METHYLON phenolic resin available from Occidental Chemicals, organosilanes such as epoxy, mercapto or amino functional silanes such as A-187 and A-1100 available from Osi -9- Specialties. An adhesion promoter can be used in an amount from 0.1 to weight percent based upon total weight of the formulation. [027] A plasticizer can be used in the present compositions in an amount ranging from 1 to 8 weight percent based upon total weight of the formulation. Useful plasticizers include phthalate esters, chlorinated paraffins, hydrogenated terphenyls, etc, {028] The formulation can further comprise one or more organic solvents, such as isopropyl alcohol, in an amount ranging from 0 to 15 percent by weight on a basis of total weight of the formulation, such as less than 15 weight percent or less than 10 weight percent. [029] Compositions of the present invention can also optionally include other additives standard in the art, such as pigments; thixotropes; retardants; catalysts; and masking agents. [030] Useful pigments include those conventional in the art, such as carbon black and metal oxides. Pigments can be present in an amount from . about 0.1 to about 10 weight percent based upon total weight of the formulation. [031] Thixotropes, for example fumed silica or carbon black, can be used in an amount from about 0.1 to about 5 weight percent based upon total weight of the formulation, [032] The curing agent will generally comprise 2 to 30 weight percent of the total composition such as 5 to 20 weight percent, with weight percent based on the total weight of the composition, in general, the equivalent ratio of curing agent to polymer blend may range from 0.5:1 to 2.0:1. A cure accelerator, if used, can be present in an amount ranging from 1 to 7 weight percent, a cure retarder, if used, in an amount ranging from 0.1 to 1 weight percent, and a moisture remover, if used, in an amount ranging from 0.1 to 1.5 weight percent, with weight percent based on the total weight of the curing agent composition. [033] When used, additives can comprise up to 50 weight percent of the total weight of the preformed composition. [034] In certain embodiments, the preformed compositions of the present invention are prepared as two pack or "2K" systems, in which the polymer blend is in one component, referred to herein as the base composition, and the curing agent is In the other component, referred to herein as the curing agent composition, The base composition and curing agent composition are mixed just prior to use. [035] The present invention is also directed to a preformed composition in shaped form comprising a polymer blend comprising at feast one polyepoxide component and at least one polythloether component, and at least one electrically conductive filler. An "electrically conductive filler" is a filler that, when added to a formulation, imparts electrical conductivity and/or EMI and/or RFI shielding to the formulation. Examples of such fillers include electrically conductive noble metal-based fillers such as pure silver; noble metal-plated noble metals such as silver-plated gold; noble metal-ptated non-noble metals such as silver plated cooper, nickel or aluminum, for example, silver-plated aluminum core particles or platinum-plated copper particles; noble-metal plated glass, plastic or ceramics such as silver-plated glass microspheres, noble-metal plated aluminum or noble-metal plated plastic microspheres; noble-metal plated mica; and other such noble-metal conductive fillers. Non-noble metal-based materials can also be suitable including non-noble metal-plated non-noble metals such as copper-coated iron particles or nickel plated copper; non-noble metals, e.g., copper, aluminum, nickel, cobalt; and non-noble-metal-plated-non metals, e.g., nickel-plated graphite and non-metal materials such as carbon black and graphite. Combinations of the conductive fillers can also be used to meet the desired conductivity, EMI/RFI shielding effectiveness, hardness and other properties suitable for a particular application. [036] The shape and size of the electrically conductive fillers is not critical to preformed compositions of the invention. The fillers may be of any shape generally used in the manufacture of conductive materials, including spherical, flake, platelet, irregular or fibrous, such as milled or chopped fibers. In making preformed compositions in shaped form, in accordance with certain embodiments of the invention, the composition may comprise conductive fillers and radar absorbing materials having various shapes. For example, the shape of the conductive fillers may be spherical, substantially spherical, or irregular. [037] Carbon fibers, particularly graphitized carbon fibers, can be used to impart electrical conductivity to preformed compositions of the invention. Carbon fibers formed by vapor phase pyrolysis methods and graphitized by heat treatment and which are hollow or solid with a fiber diameter of from 0.1 micron to several microns have high electrical conductivity. As disclosed in U.S. Patent No, 6,184,280, carbon microfibers, nanotubes or carbon fibrils having an outer diameter of less than 0.1 micron to tens of nanometers can be used as electrically conductive fillers. An example of graphitized carbon fiber suitable for conductive preformed compositions of the invention is PANEX 30MF, a 0.921 micron diameter round fiber having an electrical resistivity of 0,00055 Q-centimeter (cm). [038] The average particle size of the electrically conductive fillers can be within the range normally used for fillers in conductive materials. In certain embodiments, the particle size of the one or more fillers is from about 0.25 microns to about 250 microns, and in other embodiments from about 0.25 microns to about 75 microns, and in still other embodiments from about 0.25 microns to about 60 microns. In certain embodiments, the preformed composition of the invention comprises Ketjen Black EC-600 JD (Akzo Nobel), a conductive carbon black characterized by an iodine absorption of 1000-11500 mg/g (JO/84-5 test method), and a pore volume of 480-510 cm3/100 gm (DBF absorption. KTM 81-3504). In other embodiments, the carbon black filler is Black Pearls 2000 (Cabot Corporation), [039] In certain embodiments, electrically conductive polymers can be used to impart or modify the electrical conductivity of preformed compositions of the invention. Polymers having sulfur atoms incorporated into aromatic groups or adjacent to double bonds, such as in polyphenylene sulfide and polythiophene, are known to be electrically conductive. Other electrically conductive polymers include polypyrroles. polyaniline, poly(p-phenylene) vinyfene, and polyacetylene. All of these can be used according to the present invention. [040] In certain embodiments, electrically conductive preformed compositions of the invention comprise electrically conductive materials ranging from 2 percent to 50 percent by weight of the total weight of the electrically conductive preformed composition. [041 ] Galvanic corrosion of dissimilar metal surfaces and the electrically conductive compositions of the invention can be minimized or prevented by adding corrosion inhibitors to the composition, and/or by selecting appropriate conductive fillers. Corrosion inhibitors include, for example, strontium chromate, calcium chromate, magnesium chromate, and combinations thereof, aromatic triazoles and a sacrificial oxygen scavenger such as Zn; other suitable corrosion inhibitors are known in the art. In certain embodiments, the corrosion inhibitor comprises less than 10 percent by weight of the total weight of the electrically conductive preformed composition. In other embodiments, the corrosion inhibitor comprises an amount ranging from 2 percent to 15 percent by weight of the total weight of the electrically conductive preformed composition. Corrosion between dissimilar metal surfaces can also be minimized or prevented by the selection of the type, amount, and properties of the conductive fillers comprising the preformed composition. [042] In certain embodiments, a base composition can be prepared by batch mixing at least one polysurfide, at least one polythioether, additives, and/or fillers in a double planetary mixer under vacuum. Other suitable mixing equipment includes a kneader extruder, sigma mixer, or double "A" arm mixer. For example, a base composition can be prepared by mixing at least one polysulfide, at least one polythioether polymer, plasticizer, and phenolic adhesion promoter, After the mixture is thoroughly blended, additional constituents can be separately added and mixed using a high shear grinding blade, such as a Cowls blade, until cut it. Examples of additional constituents that can be added to a base composition include corrosion inhibitors, nonconductive fillers, electrically conductive fiber, electrically conductive flake, and silane adhesion promoters. The mixture can then be mixed for an additional 15 to 20 minutes under a vacuum of 27 inches of mercury or greater to reduce or remove entrapped air and/or gases. The base composition can then be extruded from the mixer using a high-pressure piston ram. [043] The curing agent composition can be prepared by batch mixing the curing agent and other additives. In certain embodiments, 75 percent of the total plasticizer such as partially hydrogenated terphenyi and an accelerant such as a dipentamethylene/thiuram/polysulfide mixture are mixed in a single-shaft anchor mixer. Molecular sieve powder is then added and mixed for 2 to 3 minutes. Fifty percent of the total manganese dioxide is then mixed until cut in. Stearic acid, sodium stearate, and the remaining plasticizer are then mixed until cut in followed by the remaining 50 percent of the manganese dioxide which is mixed until cut in. Fumed silica is then mixed until cut In. If the mixture is too thick, a surfactant may be added to increase wetting. The curing agent composition is then mixed for 2 to 3 minutes, passed over a three-roll paint mill to achieve a grind, and returned to the single-shaft anchor mixer and mixed for an additional 5 to 10 minutes. The curing agent composition can then be removed from the mixer with a piston ram and placed into storage containers and aged for at least five days prior to combining with a base composition. [044] The base composition and curing agent composition are mixed together to form the preformed composition just prior to use. Any suitable means for mixing can be employed, For example, the base composition and curing agent composition can be combined in the desired ratio using meter mix equipment fitted with a dynamic mix head. Pressure from the meter mix equipment forces the base and curing agent compositions through the dynamic mix head and an extrusion die. In certain embodiments the preformed composition is extruded into a laminar form including a tape or sheet. The preformed composition in sheet form can be cut to any desired shape such as the shape defined by the dimensions of an aperture to be sealed. In certain embodiments, the shaped form can be coiled with release paper separating each ring for packaging purposes. The shaped form is then refrigerated by placing the shaped form on a bed of dry ice and placing another layer of dry ice on the top of the shaped form. The shaped form is refrigerated immediately after mixing the base composition and the curing agent composition. The shaped form remains exposed to the dry ice for 5 to 15 minutes and Is then placed at a storage temperature of -40°C or lower. The term "refrigerated" refers to reducing the temperature of the preformed composition so as to retard and/or stop the curing of the preformed composition. Typically, the preformed composition in shaped form is refrigerated below ~40°C. [045] In certain embodiments, the temperature of the preformed composition is raised to a use temperature ranging from 4°C to 32°C (40°F to 90°F) prior to application. This is done such that the preformed composition reaches use temperature for no more than 10 minutes prior to application. [046] In certain embodiments the preformed composition in shaped form can be used to seal an aperture between a removable access panel and the surface adjacent to the perimeter of an opening in an aircraft fuselage. Adhesion promoter is first brushed on the perimeter of the access panel opening after the surface has been cleaned with a cleaning solvent such as DESOCLEAN. The surface of the access panel is then cleaned and coated with a release agent prior to applying the preformed composition. The preformed composition in shaped form is manually applied to the surface adjacent to the perimeter of the access panel opening, to the surface adjacent to the perimeter of the access panel, or to both. The access panel is then put in place and clamped down forcing the excess preformed composition around the edges of the access panel. Excess preformed composition is easily removed by using, for example, a flat surface. Excess preformed composition can be removed either prior to curing or after the preformed composition has cured, and preferably after the preformed composition cures. [047] The integrity, moisture resistance and fuel resistance of the seal resulting from application of preformed compositions of the present invention can be evaluated by performing the tests identified in specification MMS 332. An acceptable seal will be tight and resistant to moisture and aircraft fuel. [048] In addition to ease of handling and use, the present compositions may cause minimal corrosion to conductive surfaces in the environments encountered in aviation and aerospace applications. Because the present polymer btends have both a polysulfide and a polythioether component, they are compatible with other sealants or coating layers having one or the other of these technologies. They also exhibit good solvent resistance, [049] It is noted that, as used in this specification and the appended claims, the singular forms "a", "an", and, "the" include plural referents unless expressly and unequivocally limited to one referent. Thus, for example, reference to "a filler" includes one or more filters. Also it \s noted that, as used herein, the term "polymer" is meant to refer to prepolymers, polymers, oligomers, homopoiymers, and copolymers. [050] For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities of ingredients or percentages or proportions of other materials, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. [051] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, ail ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein. For example, a range of "10 to 50" includes any and all sub-ranges between (and including) the minimum value of 10 and the maximum value of 50, that is, any and all sub-ranges having a minimum value of equal to or greater than 10 and a maximum value of equal to or less than 50, e.g., 25 to 50, EXAMPLE [052] The following example is intended to illustrate the invention, and should not be construed as limiting the invention in any way. Example 1 [053] Example 1 provides an electrically conductive preformed composition in shaped form exhibiting EMI/RFI shielding effectiveness. The following materials were mixed in the proportions according to Table I to provide an electrically conductive base composition: PERMAPOL P 3.1 polythioether polymer from PRC-DeSoto International, Inc., THIOPLAST G4 polysulfide polymer from Akcros Chemicals (New Brunswick, New Jersey), phenolic resin adhesion promoter from PRC-DeSoto International, Inc., and HB-40 modified polyphenyl plasticizer from Solutia, Inc. (St. Louis, Missouri). Using a high shear grinding blade (Cowls blade), the following materials were individually added and blended until cut in: calcium chromate corrosion inhibitor (Wayne Pigment Corp., Milwaukee, Wisconsin), hydrophobic fumed silica (R202. from Aerosil/Degussa, Diamond Bar, California), Ni fiber (30 urn diameter, 500 Mm length; from Intramicron, Birmingham. Alabama), Ni-coated graphite (I) (60% Nicoated graphite; from Novamet, Wyckoff, New Jersey), Ni-coated graphite (II) (60% Ni-coated graphite; from Sulzer Metco/Ambeon, Switzerland), mercapto silane adhesion promoter (Silane A189; GE Specialty Materials, Wilton, CN). and epoxy silane adhesion promoter (Silane A187; GE Specialty Maten'als, Wilton, CN). (Table Removed) [054] Separately, the following materials were mixed in the amounts according to Table II to form a curing agent composition: manganese dioxide from EaglePicher (Phoenix, Arizona), partially hydrogenated terphenyl, stearic acid, fumed silica, sodium stearate from Witco Chemicals, molecular sieve powder to remove excess moisture from the curing agent, and dipentamethylene/thiuram/polysulfide mixture from Akrochem Corporation (Akron, Ohio) to acceterate the cure. The curing agent composition was allowed to set or age fro at least five days before combining with the base composition. (Table Removed) [055] One hundred parts by weight of the electrically conductive base composition according to Table I, and 10 parts by weight of the curing agent composition of Table II were combined to prepare the electrically conductive preformed composition. After thorough mixing and degassing, the electrically conductive preformed composition thus formed was extruded into a tape form and refrigerated at -40°C. [056] The surface adjacent to the perimeter of an aircraft access panel was first coated with low VOC epoxy primer according to specification MMS-423 and cured. The surface was cleaned and then coated with adhesion promoters PR-148 or PR-184 from PRC-DeSoto International, Inc. The access panel was made from titanium alloy conforming to AMS-T-9046. After the refrigerated electrically conductive preformed composition equilibrated to use temperature, 4°C to 32°C (40°F to 90°F), the electrically conductive preformed composition in tape form was manually applied to the surface adjacent to the perimeter of the access panel. The access panel was put in place to cover the access opening and clamped down, forcing the excess electrically conductive preformed composition around the edges of the access panel to fill the aperture. Excess electrically conductive preformed composition was easily removed. After 3 to 4 hours at a temperature of 4°C to 32°C (40°F to 90°F), a tight seal, resistant to moisture and aircraft fuel, resulted. [057] The cured sealant exhibited a sheet resistance (four-point probe) of less than 0.50 Q/cm. Seals to apertures between an aluminum test fixture and a carbon/epoxy lid exhibited shielding effectiveness from 1 MHz to 200 MHz when tested in an anechoic chamber. Similarly sealed apertures also exhibited shielding effectiveness from 0.1 GHz to 18 GHz when tested in a stirred mode chamber. [058J Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims. We Claim: 1. A preformed composition in shaped form consisting of a polymer blend, comprising: (A) (a) at least one polysulfide component, (b) at least one polythioether component wherein the ratio of a:b in the polymer blend is from 10:90 to 90:10 (B) a blend of additives comprising substantially equal amount of mica and polyamide, wherein the blend of additives is present in an amount of up to 50 weight percent of the total weight of the preformed composition. 2. The preformed composition as claimed in claim 1, wherein the ratio of a:b in the polymer blend is preferably 50:50. 3. The preformed composition in shaped form as claimed in claim 1, consisting of, if desired, at least one electrically conductive filler. 4. The preformed composition as claimed in claim 3, wherein the electrically conductive filler is present in an amount ranging from 2 percent to 50 percent by weight of the total weight of the electrically conductive preformed composition. 5. The preformed composition as claimed in claim 3, wherein the filler is selected from carbon, graphite, metal and conductive polymer. 6. The preformed composition as claimed in claim 3, wherein the electrically conductive filler comprises at least carbon fiber and/or carbon black. 7. The preformed composition as claimed in claim 3, wherein the composition comprises at least one corrosion inhibitor. 8. The preformed composition as claimed in claims 1 or 3, wherein the composition comprises of a curing agent for the polymer blend. 9. The preformed composition as claimed in claim 8, wherein the curing agent comprises an oxidizing agent. 10. The preformed composition as claimed in claim 9, wherein the curing agent comprises manganese dioxide. 11. The preformed composition as claimed in claim 8, wherein the curing agent is reactive at a temperature ranging from 10°C to 80°C. 12. The preformed composition as claimed in claim 8, wherein the polymer blend is present in an amount ranging from 20 percent by weight to 30 percent by weight of the total weight of the preformed composition in as much claim 8 depends on claim 1 or in an amount ranging from 20 percent by weight to 50 percent by weight of the total weight of the preformed composition in as much claim 8 depends on claim 3. 13. The preformed composition as claimed in claim 8, wherein the curing agent is present in an amount ranging from 5 percent by weight to 20 percent by weight of the total weight of the preformed composition. 14. The preformed composition as claimed in claims 1 or 3, wherein the preformed composition is curable at a temperature ranging from 10°C to 30°C. 15. The preformed composition as claimed in claim 1, wherein the composition comprises one or more additives selected from fillers, adhesion, promoters, solvents, plasticizers, thixotropes, retardants, catalysts and masking agents. 16. The preformed composition as claimed in claims 1 or 3 wherein the composition comprises plasticizer. 17. The preformed composition in shaped form as claimed in any of preceding claims 1 to 16 for use in the sealing and/or shielding of an aperture.

Full Text

PREFORMED COMPOSITIONS IN SHAPED FORM
COMPRISING POLYMER BLENDS
FIELD OF THE INVENTION
[001] The present Invention relates to preformed compositions in
shaped form and the use of preformed compositions for sealing apertures.
BACKGROUND OF THE INVENTION
[002] Electromagnetic interference can be defined as undesired
conducted or radiated electrical disturbances from an electrical or electronic
source, including transients, that can interfere with the operation of other
electrical or electronic apparatus. Such disturbances can occur at frequencies
throughout the electromagnetic spectrum. Radio frequency interference ("RFI")
is often used interchangeably with electromagnetic interference ("EMI"), although
RFI more property refers to the radio frequency portion of the electromagnetic
spectrum usually defined as 10 kilohertz (KHz) to 100 gigahertz (GHz).
[003] Electronic equipment is typically enclosed in a housing. The
housing not only serves as a physical barrier to protect the equipment from the
environment, but also can serve to shield EMI/RFJ radiation. Enclosures having
the ability to absorb and/or reflect EMI/RFI energy may be employed to confine
the EMI/RFI energy within the source device, and to Insulate the device or other
external devices from other EMI/RFI sources. To maintain accessibility to the
internal components, most enclosures are provided with openable or removable
accesses such as doors, hatches, panels, or covers. Gaps typically exist
between the accesses and the corresponding mating surfaces that reduce the
efficiency of the electromagnetic shielding by presenting openings through which
radiant energy may be emitted. Such gaps also present discontinuities in the
surface and ground conductivity of the housing, and in some cases may
generate a secondary source of EMI/RFI radiation by functioning as a slot
antenna.
[004] For filing gaps between the mating surfaces of the housing and
removable accesses, gaskets and other seals are used to maintain electrical
continuity across the structure, and to exclude environmental degradants such
as particulates, moisture, and corrosive species. Such seals are bonded or
mechanically attached to one or both of the mating surfaces and function to
establish a continuous conductive path by conforming to surface irregularities
under an applied pressure,
[005] Conventional processes for manufacturing EMI/RFI shielding
gaskets include extrusion, molding, and die-cutting. Molding involves the
compression or injection molding of an uncured or thermoplastic resin into a
certain configuration. Die-cutting involves the forming of a gasket from a cured
polymeric material, which is cut or stamped into a certain configuration using a
die. Form-in-place (TIP") processes are also used for forming EMI/RFI
shielding gaskets wherein the process involves the application of a bead of a
viscous, curable, electrically-conductive composition in a fluent state to a surface
that is subsequently cured-in-place by the application of Heat, atmospheric
moisture, or ultraviolet radiation to form an electrically-conductive, EMI/RFI
shielding gasket.
[006] Electrical conductivity and EMI/RFI shielding effectiveness is
typically Imparted to polymeric gaskets by incorporating conductive materials
within the polymer matrix. The conductive elements can include metal or metalplated
particles, fabrics, meshes, and fibers. The metal can be in the form of, for
example, filaments, particles, flakes, or spheres. Examples of metals include
copper, nickel, silver, aluminum, tin, and steel. Other conductive materials that
are used to impart EMI/RFI shielding effectiveness to polymer compositions
include conductive particles or fibers comprising carbon or graphite. Conductive
polymers such as polythiophenes, polypyrroles, polyaniline, poly(pphenylene)
vinylene, polyphenylene sulffde, polyphenylene, and polyacetylene
may also be used.
[007] In addition to shielding EMI/RFI radiation, in certain applications it
is also desirable that the seal be transparent to incident broad spectrum radiation
used for detection, location, or recognition purposes. For example, microwave
radiation from 5-18 GHz, 35 GHz, 94 GHz. 140 GHz and 220 GHz has useful
military significance. Electromagnetic radiation incident on a surface will be
partly reflected and partly absorbed by the material and the sum of these effects
determines the shielding effectiveness. The shielding effectiveness depends on
several factors including the frequency of the electromagnetic radiation, the
conductivity of the shielding material, the thickness and permeability of the
shielding material, and the distance between the radiating source and the
EMI/RFI shield. At high frequencies, above about 10 GHz, shielding
effectiveness is primarily determined by the ability of the shielding material to
absorb the incident radiation. Ferromagnetic particles with high permeability
such as iron, carbonyl iron, cobalt metal alloys, and nickel metal alloys are used
as radar absorbing materials.
[008] In addition to providing continuous electrical conductivity and
EMI/RFI shielding effectiveness, in certain applications H is desirable that gasket
or seals to surfaces exposed to the environment, such as in aviation and
aerospace vehicles, not lead to corrosion of the metal surfaces. When dissimilar
metal and/or conductive composite materials are joined in the presence of an
electrolyte, a galvanic potential is established at the interface between the
dissimilar conductors. When the interfacial seal is exposed to the environment,
particularly under severe environmental conditions such as salt fog or salt fog
containing a high concentration of SO2, corrosion of the least noble of the
conductive surfaces will occur. Corrosion may lead to a degradation in the
EMI/RFI shielding effectiveness of the seal. Mechanisms other than galvanic
potentials, e.g. crevice corrosion, may also compromise the electrical and
mechanical integrity of the enclosure.
[009] Polysulfide polymers are known in the art. The production of
polysulfide polymers is characterized by Fettes and Jorzak, Industrial
Engineering Chemistry, November, 1950, on pages 2,217 to 2,223. The
commercial use of polysulfide polymers in the manufacture of sealants for
aerospace applications has long been known and commercially used.
Polysulflde sealants have been used to seal aircraft exterior fuselage because of
the high tensile strength, high tear strength, thermal resistance, and resistance
to high ultraviolet light. Polysulfide sealants have been used to seal aircraft fuel
tanks because of the resistance to fuel and adhesion upon exposure to fuel.
[010] Polysulfide sealants are generally applied by extrusion using a
gun. Extruding a sealant to seal apertures in airframe such as those associated
with access doors or panels can require a significant amount of effort. The
interior perimeter of the access door opening is masked and the exterior
perimeter of the access door is coated with a release agent to avoid sealing an
access door shut. The sealant is extruded and the access door is put In place
and clamped down to force the excess sealant around the access door. The
sea/ant is allowed to cure and the excess sealant is trimmed away. This process
is time intensive and can add significant labor demands for servicing aircraft with
many access doors. Some aircraft can have as many as a hundred or more
access doors that are used to cover sensitive electronic equipment or fittings that
must be periodically accessed.
[011] Accordingly, it is desirable to provide compositions and methods
for sealing access doors, for example those in an airfrarne of an aviation or
aerospace vehicle, that are not as labor and time intensive as the conventional
extrusion method for sealing the access doors. It is also desirable to provide
such compositions and methods that further provide effective EMI/RFI shielding
and cause minimal corrosion to conductive surfaces.
SUMMARY OF THE INVENTION
[012] The present invention is directed to preformed compositions in
shaped form, comprising a polymer blend that comprises at least one polysulfide
component and at least one polythioether component.
[013] The present invention is further directed to methods for sealing an
aperture comprising: (a) covering the aperture with the preformed composition
of the present invention in shaped form; and (b) curing the composition so as to
seal the aperture.
DETAILED DESCRIPTION OF THE INVENTION
[014] The present invention is directed to a preformed composition in
shaped form comprising a polymer blend comprising at least one polysulfide
component and at least one polythioether component. The term "preformed11
refers to a composition that can be made into a particular shape for ease of
packaging, storage, and/or application. A composition that is preformed can be
reshaped into any shape, either intentionally, or as a result of shipping and/or
handling. The term "shaped form" refers to a configuration such that the
thickness of the preformed composition is substantially less than the lateral
dimension and includes but is not limited to tapes, sheets and cut-out or gasket
forms. The "shaped form" can be in the form of a tape meaning a narrow shape,
strip, or band that can be stored as rolls, coils, or strips. The "shaped form" can
also be die-cut to the dimensions of the aperture to be sealed.
[015] "Sealant" and like terms refer to compositions that have the ability
to resist atmospheric conditions such as moisture and/or temperature and/or at
least partially block tne transmission of materials such as water, fuel, and/or
other liquids and gasses. Sealants often have adhesive properties, as well.
"Aperture" refers to a hole, gap, slit or other opening. The term "elongated
aperture" refers to such an opening in which the length is at least three-times the
width. "Shielding" and like terms refer to the ability to divert, route, and/or reflect
incident electromagnetic energy. Shielding effectiveness represents the ratio of
the electromagnetic energy passing through a shield to the electromagnetic
energy striking the shield.
[016] The polymer blend of the present invention comprises at least
one polysulfide component and at least one polythioether component. The
"polysulfide component" of the present invention comprises a polysulfide
polymer that contains multiple sulfur-sulfur linkages, i.e., —[S—S]—, in the
polymer backbone and/or in the terminal or pendant positions on the polymer
chain. Typically, the polysulfide polymers in the present invention will have two
or more sulfur-sulfur linkages. Suitable polysulfides are commercially available
from Akzo Nobel under the name THIOPLAST. THIOPLAST products are
available in a wide range of molecular weights ranging, for example, from less
than 1100 to over 8000, with molecular weight being the average molecular
weight in grams per mole. Particularly suitable as a number average molecular
weight of 1000 to 4000. The crosslink density of these products also varies,
depending on the amount of crosslinking agent used. The "—SH" content, i.e.
the mercaptan content, of these products can also vary. The mercaptan content
and molecular weight of the polysulfide can affect the cure speed of the blend,
with cure speed increasing with molecular weight.
[017] In some embodiments, it is desired to use a combination of
pojysulfides to achieve the desired molecular weight and/or crosslink density in
the polymer blend. Different molecular weights and/or crosslink densities can
contribute different characteristics to the blend and compositions incorporating
the blend. For example, blends wherein the polysulfide component comprises
more than one polysulfide polymer and one of the polysulfide polymers has a
molecular weight of approximately 1000 have desirable non-crystallization
properties.
[018] The second component in the polymer blend of the present
invention is a polythioether. The "polythioether component" of the present
invention is a polymer comprising at least one polythioether linkage, i.e.,
-[—CHa—GHz—S—CHz—CHr-]-. Typical polythioethers have from 8 to 200 of
these linkages. Polythioethers suitable for use in the present invention indude
those described in U.S. Patent No. 6,372,849. Suitable polythioethers typically
have a number average molecular weight of 1000 to 10,000, such as 2,000 to
5,000, or 3,000 to 4,000. In some embodiments, the polythioether component
will be terminated with non-reactive groups, such as alkyl, and in other
embodiments will contain reactive groups in the terminal or pendant positions.
Typical reactive groups are thiol, hydroxyl, amino, vinyl and epoxy. For a
polythioether component that contains reactive functional groups, the average
functionality typically ranges from 2.05 to 3.0, such as from 2.1 to 2.6. A specific
average functionality can be achieved by suitable selection of reactive
ingredients. Examples of suitable polyth/oethers are available from PRC-Desoto
international, Inc., under the trademark PERMAPOL, such as PERMAPOL P-
3.1 E or PERMAPOL P-3. As with the polysulfide component, combinations of
polythioethers can be used to prepare the polythroether component according to
the present invention.
[019] The polymer blends of the present invention can be prepared
according to any standard means known in the art, such as by mixing the
polysulfide component and polythioether component and blending in a standard
mixer such as a cowls mixer or planetary mixer. The ratio of polysulfide
component to polythioether component in the blend can range from 10:90 to
90:10. A 50:50 ratio is particularly suitable for some embodiments. The
molecular weight of the present polymer blend is typically from 1000 to 8000,
such as 3500 to 4500, as measured theoretically or using GPC. The Tg of the
polymer blend is typically ~70°C or lower, such as -60°C or lower. The viscosity
of the blend will typically be lower than the viscosity of a polysulfide having a
comparable molecular weight; this contributes to the ease of handling of the
present compositions and may minimize if not eliminate the need for solvents.
1020] The polymer blend in the present compositions typically
comprises 10 to 50 weight percent, such as 20 to 30 weight percent, with weight
percent based on the weight of the total preformed composition.
[021] In certain embodiments, the preformed composition of the present
invention further comprises a suitable curing agent. The term "curing agent"
refers to any material that can be added to accelerate the curing or gelling of the
polymer blend. In some embodiments, the curing agent is reactive at 10°C to
80°C. The term "reactive" means capable of chemical reaction and includes any
level of reaction from partial to complete reaction of a reactant. in certain
embodiments, a curing agent is reactive when it provides for cross-linking or
gelling of a sulfur-containing polymer. "Cure" refers to the point at which the
composition achieves a cure hardness of 30 Durometer "A" as measured
according to ASTM D2240.
[022] In certain embodiments, the preformed composition comprises a
curing agent that contains oxidizing agents that oxidize terminal mercaptan
groups in the polymer blend. Useful curing agents include lead dioxide,
manganese dioxide, calcium dioxide, sodium perborate monohydrate, calcium
peroxide, zinc peroxide, dichromate and epoxy. Other suitable curing agents
may contain reactive functional groups that are reactive with the functional
groups in the polymer blend. Examples include but are not limited to polythiols,
such as polythioethers; polyisocyanates such as isophorone diisocyanate,
hexamethylene diisocyanate, and mixtures and isocyanurate derivatives thereof;
and polyepoxides. Examples of polyepoxides include hydantoin diepoxide,
Bisphenol-A epoxides, Bisphenol-F epoxides, Novolac-type epoxides, aliphatic
polyepoxides, and epoxidized unsaturated and phenolic resins. The term
"polyepoxide" refers to a material having a 1,2-epoxy equivalent greater than one
and includes monomers, oligomers, and polymers. Cure accelerators or
retardants can also be used, such as a dimethylene/thiuram/polysulfide mixture
cure accelerator or a stearic acid cure retarder, which will retard the rate of cure
thereby extending the "pot life" of the composition. To control the properties-of
the composition, one or more materials capable of at least partially removing
moisture from the composition, such as molecular sieve powder.
[023] The preformed compositions of the present invention can also
comprise one or more additives. "Additives" refer to non-reactive components in
the preformed composition that provides a desired property. Examples of
additives include but are not limited to fillers, adhesion promoters, and
plasticizers. Fillers useful in the present compositions, especially for aerospace
applications, include those commonly used in the art, such as carbon black,
calcium carbonate (CaCO3), silica, nylon and the like. Potting compound fillers
illustratively include high band gap materials such as zinc sulfide and inorganic
barium compounds. In one embodiment, the compositions include about 10 to
about 70 weight percent of the selected filler or combination of fillers, such as
about 10 to 50 weight percent based upon the total weight of the composition. In
one embodiment, a combination of mica and polyamide are used as the filler
component.
[024] Mica is a silicate characterized by basal cleavage that imparts
flexibility to laminas. Micas include natural muscovite, phlogopite, and biotite, as
well as synthetic fluorophlogopite and barium disilicic. Preparation of synthetic
micas is described in Encyclopedia of Chemical Technology, Vol. 13, pp. 398-
424, John Wiley & Sons (1967). Mica provides flexibility and pliability to the
preformed composition and reduces the tack, Polyamide powder provides
viscosity and reduces the tack of the preformed composition. Polyamide resins
can be produced by the condensation reaction of dimerized fatty acids, such as
dimerized linoleic acid, with lower aliphatic polyamines, such as for example,
ethylene diamine or diethylene triamine, so that the final product has multiple
amide groups in the resin backbone. A process for the manufacture of
polyamide resins is disclosed in U,S. Patent No. 2,450,940. Polyamide resins
. suitable for the preformed composition are solid at use temperature and typically
have a number average molecular weight of at least 10,000 Daltons.
[025] In certain embodiments, mica and polyamide together form 10
percent by weight to 50 percent by weight of the total weight of the preformed
composition with substantially equal amounts of mica and polyamide.
"Substantially equal" means that the amount of mica and the amount of
polyamide are present in an amount of less than 5 percent of each other. The
amount of mica can range from 5 percent by weight to 25 percent by weight and
the amount of polyamide from 5 percent by weight to 25 percent by weight. In
one embodiment, the amount of mica ranges from 10 percent by weight to 20
percent by weight and the amount of polyamide ranges from 10 percent by
weight to 20 percent by weight of the total weight of the preformed composition.
[026] One or more adhesion promoters can also be used. Suitable
adhesion promoters include phenolics such as METHYLON phenolic resin
available from Occidental Chemicals, organosilanes such as epoxy, mercapto or
amino functional silanes such as A-187 and A-1100 available from Osi
-9-
Specialties. An adhesion promoter can be used in an amount from 0.1 to
weight percent based upon total weight of the formulation.
[027] A plasticizer can be used in the present compositions in an
amount ranging from 1 to 8 weight percent based upon total weight of the
formulation. Useful plasticizers include phthalate esters, chlorinated paraffins,
hydrogenated terphenyls, etc,
{028] The formulation can further comprise one or more organic
solvents, such as isopropyl alcohol, in an amount ranging from 0 to 15 percent
by weight on a basis of total weight of the formulation, such as less than 15
weight percent or less than 10 weight percent.
[029] Compositions of the present invention can also optionally include
other additives standard in the art, such as pigments; thixotropes; retardants;
catalysts; and masking agents.
[030] Useful pigments include those conventional in the art, such as
carbon black and metal oxides. Pigments can be present in an amount from
. about 0.1 to about 10 weight percent based upon total weight of the formulation.
[031] Thixotropes, for example fumed silica or carbon black, can be
used in an amount from about 0.1 to about 5 weight percent based upon total
weight of the formulation,
[032] The curing agent will generally comprise 2 to 30 weight percent of
the total composition such as 5 to 20 weight percent, with weight percent based
on the total weight of the composition, in general, the equivalent ratio of curing
agent to polymer blend may range from 0.5:1 to 2.0:1. A cure accelerator, if
used, can be present in an amount ranging from 1 to 7 weight percent, a cure
retarder, if used, in an amount ranging from 0.1 to 1 weight percent, and a
moisture remover, if used, in an amount ranging from 0.1 to 1.5 weight percent,
with weight percent based on the total weight of the curing agent composition.
[033] When used, additives can comprise up to 50 weight percent of
the total weight of the preformed composition.
[034] In certain embodiments, the preformed compositions of the
present invention are prepared as two pack or "2K" systems, in which the
polymer blend is in one component, referred to herein as the base composition,
and the curing agent is In the other component, referred to herein as the curing
agent composition, The base composition and curing agent composition are
mixed just prior to use.
[035] The present invention is also directed to a preformed composition
in shaped form comprising a polymer blend comprising at feast one polyepoxide
component and at least one polythloether component, and at least one
electrically conductive filler. An "electrically conductive filler" is a filler that, when
added to a formulation, imparts electrical conductivity and/or EMI and/or RFI
shielding to the formulation. Examples of such fillers include electrically
conductive noble metal-based fillers such as pure silver; noble metal-plated
noble metals such as silver-plated gold; noble metal-ptated non-noble metals
such as silver plated cooper, nickel or aluminum, for example, silver-plated
aluminum core particles or platinum-plated copper particles; noble-metal plated
glass, plastic or ceramics such as silver-plated glass microspheres, noble-metal
plated aluminum or noble-metal plated plastic microspheres; noble-metal plated
mica; and other such noble-metal conductive fillers. Non-noble metal-based
materials can also be suitable including non-noble metal-plated non-noble
metals such as copper-coated iron particles or nickel plated copper; non-noble
metals, e.g., copper, aluminum, nickel, cobalt; and non-noble-metal-plated-non
metals, e.g., nickel-plated graphite and non-metal materials such as carbon
black and graphite. Combinations of the conductive fillers can also be used to
meet the desired conductivity, EMI/RFI shielding effectiveness, hardness and
other properties suitable for a particular application.
[036] The shape and size of the electrically conductive fillers is not
critical to preformed compositions of the invention. The fillers may be of any
shape generally used in the manufacture of conductive materials, including
spherical, flake, platelet, irregular or fibrous, such as milled or chopped fibers. In
making preformed compositions in shaped form, in accordance with certain
embodiments of the invention, the composition may comprise conductive fillers
and radar absorbing materials having various shapes. For example, the shape
of the conductive fillers may be spherical, substantially spherical, or irregular.
[037] Carbon fibers, particularly graphitized carbon fibers, can be used
to impart electrical conductivity to preformed compositions of the invention.
Carbon fibers formed by vapor phase pyrolysis methods and graphitized by heat
treatment and which are hollow or solid with a fiber diameter of from 0.1 micron
to several microns have high electrical conductivity. As disclosed in U.S. Patent
No, 6,184,280, carbon microfibers, nanotubes or carbon fibrils having an outer
diameter of less than 0.1 micron to tens of nanometers can be used as
electrically conductive fillers. An example of graphitized carbon fiber suitable for
conductive preformed compositions of the invention is PANEX 30MF, a 0.921
micron diameter round fiber having an electrical resistivity of
0,00055 Q-centimeter (cm).
[038] The average particle size of the electrically conductive fillers can
be within the range normally used for fillers in conductive materials. In certain
embodiments, the particle size of the one or more fillers is from about 0.25
microns to about 250 microns, and in other embodiments from about 0.25
microns to about 75 microns, and in still other embodiments from about 0.25
microns to about 60 microns. In certain embodiments, the preformed
composition of the invention comprises Ketjen Black EC-600 JD (Akzo Nobel), a
conductive carbon black characterized by an iodine absorption of 1000-11500
mg/g (JO/84-5 test method), and a pore volume of 480-510 cm3/100 gm (DBF
absorption. KTM 81-3504). In other embodiments, the carbon black filler is
Black Pearls 2000 (Cabot Corporation),
[039] In certain embodiments, electrically conductive polymers can be
used to impart or modify the electrical conductivity of preformed compositions of
the invention. Polymers having sulfur atoms incorporated into aromatic groups
or adjacent to double bonds, such as in polyphenylene sulfide and
polythiophene, are known to be electrically conductive. Other electrically
conductive polymers include polypyrroles. polyaniline, poly(p-phenylene)
vinyfene, and polyacetylene. All of these can be used according to the present
invention.
[040] In certain embodiments, electrically conductive preformed
compositions of the invention comprise electrically conductive materials ranging
from 2 percent to 50 percent by weight of the total weight of the electrically
conductive preformed composition.
[041 ] Galvanic corrosion of dissimilar metal surfaces and the electrically
conductive compositions of the invention can be minimized or prevented by
adding corrosion inhibitors to the composition, and/or by selecting appropriate
conductive fillers. Corrosion inhibitors include, for example, strontium chromate,
calcium chromate, magnesium chromate, and combinations thereof, aromatic
triazoles and a sacrificial oxygen scavenger such as Zn; other suitable corrosion
inhibitors are known in the art. In certain embodiments, the corrosion inhibitor
comprises less than 10 percent by weight of the total weight of the electrically
conductive preformed composition. In other embodiments, the corrosion
inhibitor comprises an amount ranging from 2 percent to 15 percent by weight of
the total weight of the electrically conductive preformed composition. Corrosion
between dissimilar metal surfaces can also be minimized or prevented by the
selection of the type, amount, and properties of the conductive fillers comprising
the preformed composition.
[042] In certain embodiments, a base composition can be prepared by
batch mixing at least one polysurfide, at least one polythioether, additives, and/or
fillers in a double planetary mixer under vacuum. Other suitable mixing
equipment includes a kneader extruder, sigma mixer, or double "A" arm mixer.
For example, a base composition can be prepared by mixing at least one
polysulfide, at least one polythioether polymer, plasticizer, and phenolic
adhesion promoter, After the mixture is thoroughly blended, additional
constituents can be separately added and mixed using a high shear grinding
blade, such as a Cowls blade, until cut it. Examples of additional constituents
that can be added to a base composition include corrosion inhibitors, nonconductive
fillers, electrically conductive fiber, electrically conductive flake, and
silane adhesion promoters. The mixture can then be mixed for an additional 15
to 20 minutes under a vacuum of 27 inches of mercury or greater to reduce or
remove entrapped air and/or gases. The base composition can then be
extruded from the mixer using a high-pressure piston ram.
[043] The curing agent composition can be prepared by batch mixing
the curing agent and other additives. In certain embodiments, 75 percent of the
total plasticizer such as partially hydrogenated terphenyi and an accelerant such
as a dipentamethylene/thiuram/polysulfide mixture are mixed in a single-shaft
anchor mixer. Molecular sieve powder is then added and mixed for 2 to 3
minutes. Fifty percent of the total manganese dioxide is then mixed until cut in.
Stearic acid, sodium stearate, and the remaining plasticizer are then mixed until
cut in followed by the remaining 50 percent of the manganese dioxide which is
mixed until cut in. Fumed silica is then mixed until cut In. If the mixture is too
thick, a surfactant may be added to increase wetting. The curing agent
composition is then mixed for 2 to 3 minutes, passed over a three-roll paint mill
to achieve a grind, and returned to the single-shaft anchor mixer and mixed for
an additional 5 to 10 minutes. The curing agent composition can then be
removed from the mixer with a piston ram and placed into storage containers
and aged for at least five days prior to combining with a base composition.
[044] The base composition and curing agent composition are mixed
together to form the preformed composition just prior to use. Any suitable
means for mixing can be employed, For example, the base composition and
curing agent composition can be combined in the desired ratio using meter mix
equipment fitted with a dynamic mix head. Pressure from the meter mix
equipment forces the base and curing agent compositions through the dynamic
mix head and an extrusion die. In certain embodiments the preformed
composition is extruded into a laminar form including a tape or sheet. The
preformed composition in sheet form can be cut to any desired shape such as
the shape defined by the dimensions of an aperture to be sealed. In certain
embodiments, the shaped form can be coiled with release paper separating each
ring for packaging purposes. The shaped form is then refrigerated by placing the
shaped form on a bed of dry ice and placing another layer of dry ice on the top of
the shaped form. The shaped form is refrigerated immediately after mixing the
base composition and the curing agent composition. The shaped form remains
exposed to the dry ice for 5 to 15 minutes and Is then placed at a storage
temperature of -40°C or lower. The term "refrigerated" refers to reducing the
temperature of the preformed composition so as to retard and/or stop the curing
of the preformed composition. Typically, the preformed composition in shaped
form is refrigerated below ~40°C.
[045] In certain embodiments, the temperature of the preformed
composition is raised to a use temperature ranging from 4°C to 32°C (40°F to
90°F) prior to application. This is done such that the preformed composition
reaches use temperature for no more than 10 minutes prior to application.
[046] In certain embodiments the preformed composition in shaped
form can be used to seal an aperture between a removable access panel and
the surface adjacent to the perimeter of an opening in an aircraft fuselage.
Adhesion promoter is first brushed on the perimeter of the access panel opening
after the surface has been cleaned with a cleaning solvent such as
DESOCLEAN. The surface of the access panel is then cleaned and coated with
a release agent prior to applying the preformed composition. The preformed
composition in shaped form is manually applied to the surface adjacent to the
perimeter of the access panel opening, to the surface adjacent to the perimeter
of the access panel, or to both. The access panel is then put in place and
clamped down forcing the excess preformed composition around the edges of
the access panel. Excess preformed composition is easily removed by using, for
example, a flat surface. Excess preformed composition can be removed either
prior to curing or after the preformed composition has cured, and preferably after
the preformed composition cures.
[047] The integrity, moisture resistance and fuel resistance of the seal
resulting from application of preformed compositions of the present invention can
be evaluated by performing the tests identified in specification MMS 332. An
acceptable seal will be tight and resistant to moisture and aircraft fuel.
[048] In addition to ease of handling and use, the present compositions
may cause minimal corrosion to conductive surfaces in the environments
encountered in aviation and aerospace applications. Because the present
polymer btends have both a polysulfide and a polythioether component, they are
compatible with other sealants or coating layers having one or the other of these
technologies. They also exhibit good solvent resistance,
[049] It is noted that, as used in this specification and the appended
claims, the singular forms "a", "an", and, "the" include plural referents unless
expressly and unequivocally limited to one referent. Thus, for example,
reference to "a filler" includes one or more filters. Also it \s noted that, as used
herein, the term "polymer" is meant to refer to prepolymers, polymers, oligomers,
homopoiymers, and copolymers.
[050] For the purposes of this specification and appended claims,
unless otherwise indicated, all numbers expressing quantities of ingredients or
percentages or proportions of other materials, reaction conditions, and so forth
used in the specification and claims are to be understood as being modified in all
instances by the term "about". Accordingly, unless indicated to the contrary, the
numerical parameters set forth in the following specification and attached claims
are approximations that may vary depending upon the desired properties sought
to be obtained by the present invention. At the very least, and not as an attempt
to limit the application of the doctrine of equivalents to the scope of the claims,
each numerical parameter should at least be construed in light of the number of
reported significant digits and by applying ordinary rounding techniques.
[051] Notwithstanding that the numerical ranges and parameters setting
forth the broad scope of the invention are approximations, the numerical values
set forth in the specific examples are reported as precisely as possible. Any
numerical value, however, inherently contains certain errors necessarily resulting
from the standard deviation found in their respective testing measurements.
Moreover, ail ranges disclosed herein are to be understood to encompass any
and all sub-ranges subsumed therein. For example, a range of "10 to 50"
includes any and all sub-ranges between (and including) the minimum value of
10 and the maximum value of 50, that is, any and all sub-ranges having a
minimum value of equal to or greater than 10 and a maximum value of equal to
or less than 50, e.g., 25 to 50,
EXAMPLE
[052] The following example is intended to illustrate the invention, and
should not be construed as limiting the invention in any way.
Example 1
[053] Example 1 provides an electrically conductive preformed
composition in shaped form exhibiting EMI/RFI shielding effectiveness. The
following materials were mixed in the proportions according to Table I to provide
an electrically conductive base composition: PERMAPOL P 3.1 polythioether
polymer from PRC-DeSoto International, Inc., THIOPLAST G4 polysulfide
polymer from Akcros Chemicals (New Brunswick, New Jersey), phenolic resin
adhesion promoter from PRC-DeSoto International, Inc., and HB-40 modified
polyphenyl plasticizer from Solutia, Inc. (St. Louis, Missouri). Using a high shear
grinding blade (Cowls blade), the following materials were individually added and
blended until cut in: calcium chromate corrosion inhibitor (Wayne Pigment
Corp., Milwaukee, Wisconsin), hydrophobic fumed silica (R202. from
Aerosil/Degussa, Diamond Bar, California), Ni fiber (30 urn diameter, 500 Mm
length; from Intramicron, Birmingham. Alabama), Ni-coated graphite (I) (60% Nicoated
graphite; from Novamet, Wyckoff, New Jersey), Ni-coated graphite (II)
(60% Ni-coated graphite; from Sulzer Metco/Ambeon, Switzerland), mercapto
silane adhesion promoter (Silane A189; GE Specialty Materials, Wilton, CN). and
epoxy silane adhesion promoter (Silane A187; GE Specialty Maten'als, Wilton,
CN).
(Table Removed) [054] Separately, the following materials were mixed in the amounts
according to Table II to form a curing agent composition: manganese dioxide
from EaglePicher (Phoenix, Arizona), partially hydrogenated terphenyl, stearic
acid, fumed silica, sodium stearate from Witco Chemicals, molecular sieve
powder to remove excess moisture from the curing agent, and
dipentamethylene/thiuram/polysulfide mixture from Akrochem Corporation
(Akron, Ohio) to acceterate the cure. The curing agent composition was allowed
to set or age fro at least five days before combining with the base composition.
(Table Removed) [055] One hundred parts by weight of the electrically conductive base
composition according to Table I, and 10 parts by weight of the curing agent
composition of Table II were combined to prepare the electrically conductive
preformed composition. After thorough mixing and degassing, the electrically
conductive preformed composition thus formed was extruded into a tape form
and refrigerated at -40°C.
[056] The surface adjacent to the perimeter of an aircraft access panel
was first coated with low VOC epoxy primer according to specification MMS-423
and cured. The surface was cleaned and then coated with adhesion promoters
PR-148 or PR-184 from PRC-DeSoto International, Inc. The access panel was
made from titanium alloy conforming to AMS-T-9046. After the refrigerated
electrically conductive preformed composition equilibrated to use temperature,
4°C to 32°C (40°F to 90°F), the electrically conductive preformed composition in
tape form was manually applied to the surface adjacent to the perimeter of the
access panel. The access panel was put in place to cover the access opening
and clamped down, forcing the excess electrically conductive preformed
composition around the edges of the access panel to fill the aperture. Excess
electrically conductive preformed composition was easily removed. After 3 to 4
hours at a temperature of 4°C to 32°C (40°F to 90°F), a tight seal, resistant to
moisture and aircraft fuel, resulted.
[057] The cured sealant exhibited a sheet resistance (four-point probe)
of less than 0.50 Q/cm. Seals to apertures between an aluminum test fixture
and a carbon/epoxy lid exhibited shielding effectiveness from 1 MHz to 200 MHz
when tested in an anechoic chamber. Similarly sealed apertures also exhibited
shielding effectiveness from 0.1 GHz to 18 GHz when tested in a stirred mode
chamber.
[058J Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to those skilled in
the art that numerous variations of the details of the present invention may be
made without departing from the invention as defined in the appended claims.

We Claim:
1. A preformed composition in shaped form consisting of a polymer blend, comprising:
(A)
(a) at least one polysulfide component,
(b) at least one polythioether component
wherein the ratio of a:b in the polymer blend is from 10:90 to 90:10 (B) a blend of additives comprising substantially equal amount of mica and polyamide, wherein the blend of additives is present in an amount of up to 50 weight percent of the total weight of the preformed composition.
2. The preformed composition as claimed in claim 1, wherein the ratio of a:b in the polymer blend is preferably 50:50.
3. The preformed composition in shaped form as claimed in claim 1, consisting of, if desired, at least one electrically conductive filler.
4. The preformed composition as claimed in claim 3, wherein the electrically conductive filler is present in an amount ranging from 2 percent to 50 percent by weight of the total weight of the electrically conductive preformed composition.
5. The preformed composition as claimed in claim 3, wherein the filler is selected from carbon, graphite, metal and conductive polymer.
6. The preformed composition as claimed in claim 3, wherein the electrically conductive filler comprises at least carbon fiber and/or carbon black.
7. The preformed composition as claimed in claim 3, wherein the composition comprises at least one corrosion inhibitor.
8. The preformed composition as claimed in claims 1 or 3, wherein the composition comprises of a curing agent for the polymer blend.
9. The preformed composition as claimed in claim 8, wherein the curing agent comprises an oxidizing agent.
10. The preformed composition as claimed in claim 9, wherein the curing agent comprises manganese dioxide.
11. The preformed composition as claimed in claim 8, wherein the curing agent is reactive at a temperature ranging from 10°C to 80°C.

12. The preformed composition as claimed in claim 8, wherein the polymer blend is present in an amount ranging from 20 percent by weight to 30 percent by weight of the total weight of the preformed composition in as much claim 8 depends on claim 1 or in an amount ranging from 20 percent by weight to 50 percent by weight of the total weight of the preformed composition in as much claim 8 depends on claim 3.
13. The preformed composition as claimed in claim 8, wherein the curing agent is present in an amount ranging from 5 percent by weight to 20 percent by weight of the total weight of the preformed composition.
14. The preformed composition as claimed in claims 1 or 3, wherein the preformed composition is curable at a temperature ranging from 10°C to 30°C.
15. The preformed composition as claimed in claim 1, wherein the composition comprises one or more additives selected from fillers, adhesion, promoters, solvents, plasticizers, thixotropes, retardants, catalysts and masking agents.
16. The preformed composition as claimed in claims 1 or 3 wherein the composition comprises plasticizer.
17. The preformed composition in shaped form as claimed in any of preceding claims 1 to 16 for use in the sealing and/or shielding of an aperture.

Documents:

1668-DEL-2007-Correspondence Others-(07-12-2011).pdf

1668-delnp-2007-Abstract-(25-07-2011).pdf

1668-delnp-2007-abstract.pdf

1668-delnp-2007-assignment.pdf

1668-DELNP-2007-Claims-(07-12-2011).pdf

1668-DELNP-2007-Claims-(14-11-2011).pdf

1668-delnp-2007-Claims-(25-07-2011).pdf

1668-delnp-2007-claims.pdf

1668-delnp-2007-Correspondence Others-(03-08-2011).pdf

1668-DELNP-2007-Correspondence Others-(07-09-2011).pdf

1668-DELNP-2007-Correspondence Others-(14-11-2011).pdf

1668-delnp-2007-Correspondence Others-(25-07-2011).pdf

1668-DELNP-2007-Correspondence Others-(30-08-2011).pdf

1668-delnp-2007-correspondence-others-1.pdf

1668-DELNP-2007-Correspondence-Others.pdf

1668-delnp-2007-description (complete).pdf

1668-delnp-2007-form-1.pdf

1668-delnp-2007-form-18.pdf

1668-delnp-2007-form-2.pdf

1668-delnp-2007-Form-3-(03-08-2011).pdf

1668-DELNP-2007-Form-3-(07-09-2011).pdf

1668-DELNP-2007-Form-3.pdf

1668-delnp-2007-form-5.pdf

1668-delnp-2007-GPA-(25-07-2011).pdf

1668-delnp-2007-gpa.pdf

1668-delnp-2007-pct-101.pdf

1668-delnp-2007-pct-105.pdf

1668-delnp-2007-pct-210.pdf

1668-delnp-2007-pct-220.pdf

1668-delnp-2007-pct-237.pdf

1668-delnp-2007-pct-301.pdf

1668-delnp-2007-pct-304.pdf

1668-delnp-2007-pct-308.pdf

1668-delnp-2007-pct-332.pdf

1668-delnp-2007-pct-401.pdf

1668-delnp-2007-pct-409.pdf

1668-delnp-2007-pct-416.pdf

1668-delnp-2007-Petition-137-(03-08-2011).pdf

1668-DELNP-2007-Petition-137-(07-09-2011).pdf

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Patent Number

252126

Indian Patent Application Number

1668/DELNP/2007

PG Journal Number

18/2012

Publication Date

04-May-2012

Grant Date

27-Apr-2012

Date of Filing

01-Mar-2007

Name of Patentee

PRC-DESOTO INTERNATIONAL, INC

Applicant Address

5430 SAN FERNANDO ROAD, GLENDALE, CA 91203, USA

Inventors:

#	Inventor's Name	Inventor's Address
1	COSMAN, MICHAEL, A,	27803 SANDSTONE COURT, VALENCIA, CA 91354, USA
2	BALLADARES, ADRIAN, K.	134 VIRGINIA STREET, UNIT A, EI SEGUNDO, CA 90245, USA

PCT International Classification Number

C08L 81/02

PCT International Application Number

PCT/US2005/031695

PCT International Filing date

2005-09-02

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	10/935,857	2004-09-08	U.S.A.