structural adhesive composition and coated substrate

专利摘要:
COMPOSITION AND COATED SUBSTRATE Compositions are described here including (a) a first component containing: (1) an epoxy adduct which is the reaction product of reagents comprising a first epoxy compound, a polyol, and an anhydride and / or a diacid; and (2) a second epoxy compound; (b) rubber particles having a core / shell structure; and (c) a second component that reacts chemically with said first component under ambient or slightly thermal conditions. Also described here are compositions including (a) an epoxy capped flexibilizer; (b) a heat activated latent curing agent; and optionally, (c) beaker particles having a core / shell structure and / or graphene carbon particles; (d) an epoxy / CTBN adduct; and / or (e) an epoxy / dimer acid adduct.
公开号:BR112014013594B1
申请号:R112014013594-0
申请日:2012-12-07
公开日:2021-01-05
发明作者:Umesh C. Desai；Tien-Chieh Chao；Masayuki Nakajima；Kaliappa G. Ragunathan
申请人:Ppg Industries Ohio, Inc.；
IPC主号:

专利说明:

Field of invention
[0001] The present invention relates to structural adhesive compositions and more particularly to structural adhesive compositions 1K and 2K. Background of the invention
[0002] Structural adhesives are used in a wide variety of applications to bond two or more substrate materials together. For example, structural adhesives can be used to connect wind turbine propellers or to connect automotive structural components.
[0003] The present invention is directed to one-component adhesive compositions (1K) and two-component adhesive compositions (2K) which provide sufficient bond strength, are easy to apply and, when applicable, have sufficient durability for use in bonding. substrate materials. Summary of the invention
[0004] An embodiment of the present invention description of a composition comprising: (a) a first component containing: (1) an epoxy adduct formed as a reactant reaction product comprising a first epoxy compound, a polyol, and an anhydride and / or a diacid; and (b) rubber particles having a core / shell structure and / or graphene carbon particles; and (c) a second component that reacts chemically with the first component under ambient or slightly thermal conditions.
[0005] Another embodiment of the present invention describes a composition comprising (a) an epoxy-capped flexibilizer; and (b) a heat activated latent curing agent; and optionally (c) rubber particles having a core / shell structure and / or graphene carbon particles; (d) an epoxy / CTBN adduct; and / or (e) an epoxy acid / dimer adduct. Brief description of the figures
[0006] Figure 1 illustrates a perspective view of a teflon pattern arrangement for evaluating the tensile properties of structural adhesives according to an exemplary embodiment of the present invention. Detailed description of the invention
[0007] For the purpose of the detailed description below, it should be understood that the invention may assume several alternatives, variations and step sequences, except where expressly specified otherwise. In addition, in addition to any operational example, or where otherwise indicated, all figures expressing, for example, quantities of ingredients used in the report and claims should be understood to be modified in all examples, by the term "about" . Consequently, unless otherwise indicated, the numerical parameters represented in the following report and in the appended claims are approximations that may vary depending on the desired properties to be obtained by the present invention. At a minimum, and not as an attempt to limit the equivalents doctrine request to the scope of protection of claims, each numerical parameter must at least be constructed in light of the number of significant digits reported and by applying the ordinary rounding technique.
[0008] Although the numerical ranges and parameters representing the broad scope of the invention are approximations, the numerical values represented in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the variation in the pattern found in their respective test measurements.
[0009] Furthermore, it should be understood that any numerical range mentioned here is intended to include all the sub-ranges included here. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the minimum quoted value of 1 and the maximum quoted value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.
[0010] In this application, the use of the singular includes the plural and the plural includes the singular, unless otherwise specifically stated. In addition, in this application, the use of "or" means "and / or" unless specifically stated otherwise, although "and / or" may be explicitly used in certain examples.
[0011] As noted above, in general, the present invention describes 1K (“one component”) and 2K (“two component”) structural adhesive compositions that are used to: bond two substrate materials together for a wide variety of Potential application in which the bonding between the substrate material provides particular mechanical properties related to elongation, tensile strength, shear strength in bending, resistance to T-shape, modulus, or resistance to house impact. The structural adhesive is applied to both one and both materials being bonded. The parts are aligned and pressure and spacers can be added to control the thickness of the connection. For 2K adhesives, curing begins when mixing the components at room temperature or slightly thermal temperature. In contrast, for 1K adhesives, the adhesive is cured using an external source such as an oven (or other thermal medium) or through the use of actinic radiation (UV light, etc.).
[0012] Suitable substrate materials that can be bonded by the adhesive composition to the structure include, but are not limited to, materials such as metals or metal alloys, natural materials such as wood, polymeric materials such as hard plastics, or composite materials. The structural adhesives of the present invention are particularly suitable for use in various automotive applications and for use in wind turbine technology.
[0013] As noted, the structural adhesive compositions of the present invention are suitable for use in connection of two halves of the wind turbine blades. In this application, for a 2K adhesive, the mixed adhesive composition is applied close to the edges of one or both halves of the wind turbine blades. The halves are then pressed together and the 2K adhesive is allowed to cure for a number of hours in ambient or mildly thermal conditions. A thermal blanket (about 70 ° C) can be applied to the halves to assist in the curing process. In contrast, for 1K adhesives, as opposed to a system in which the components cure substantially during mixing, an oven or actinic radiation source is used to complete the curing process.
[0014] The halves, or other components of the blades of the wind turbine, can be formed from metals, such as aluminum, metal alloys such as steel, wood, such as balsa wood, polymeric materials such as hard plastics , or composite materials such as fiber-reinforced plastics. In one embodiment, the halves are formed from fiberglass composites or carbon fiber composites.
[0015] The 2K structural adhesives of the present invention are formed from two chemical components, called, a first component and a second component that are mixed only before application. The first component (i.e., an epoxy component), in certain embodiments, comprises an epoxy adduct and another epoxy compound, or the second epoxy compound. The second component, in certain embodiments, comprises a curing component that reacts with the first curing component to form a bond that provides the substrates to which it is applied with the desired bonding characteristics. In certain embodiments, the curing component is an amine compound, although another curing component such as sulfide curing components may alternatively be used.
[0016] The equivalent ratio of amine to epoxy in the adhesive composition can vary from about 0.5: 1 to about 1.5: 1, such as from 1.0: 1 to 1.25: 1. In certain embodiments, the equivalent ratio of amine to epoxy is slightly above 1: 1. As described here, the epoxy equivalents used in calculating the epoxy equivalent proportion are based on the epoxy equivalent weight of the first component, and the amine equivalents used in calculating the equivalent amine proportion are based on the equivalent weight of the amine hydrogen ( AHEW) of the second component.
[0017] In one embodiment, the epoxy adduct is formed as the reaction product of reagents comprising a first epoxy compound, a polyol, and an anhydride.
[0018] In another embodiment, the epoxy adduct is formed as the reaction product of reagents comprising a first epoxy compound, a polyol, and a diacid.
[0019] In yet another embodiment, the epoxy adduct is formed as the reaction product of reagents comprising a first epoxy compound, a polyol, an anhydride, and a diacid.
[0020] In these embodiments, the epoxy adduct comprises 3 to 50 weight percent, as well as 3 to 25 weight percent of the first component, while the second epoxy compound comprises 50 to 97 weight percent, such as 75 to 97 weight percent of the first component.
[0021] The first useful epoxy compounds that can be used to form an epoxy adduct include polyepoxides. Suitable polyepoxides include Bisphenol A polyglycidyl ethers, such as Epon® 828 and 1001 epoxy kingdoms, and Bisphenol F, diepoxides, such as Epon® 862, which are commercially available from Hexion Specialty Chemicals, Inc. Other useful polyepoxides include ethers of polyhydric alcohol polyglycidyl, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, and novolac epoxy resins. In still other non-limiting embodiments, the first epoxy compound includes epoxidated Bisphenol A novalac, epoxidated phenolic novolacs, epoxidated cresyl novolac, and bismaleiimide P-aminophenol triglycidyl.
[0022] Useful polyols that can be used to form the epoxy adduct include diols, triols, tetraols, and higher functional polyols. Polyols can be based on a polyether chain derived from ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and the like in mixtures thereof. The polyol can also be based on a polyester chain derived from caprolatone ring opening polymerization. Suitable polyols can also include polyether polyol, polyurethane polyol, polyurea polyol, acrylic polyol, polyester polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polycarbonate polyol, polysiloxane polyol, and combinations thereof. Polyamines corresponding to polyols can also be used, in which case, amides instead of carboxylic esters will be formed with acids and anhydrides.
[0023] Appropriate diols that can be used to form the epoxy adduct are diols having an equivalent hydroxyl weight of 30 and 1000. Examples of diols having an hydroxyl equivalent weight of 30 to 1000 include diols sold under the trade name Terathane ®, including Terathane® 250, available from Invista. Other examples of diols having a hydroxyl equivalent weight of 30 to 1000 include ethylene glycol and its polyether diols, propylene glycol and its polyether diols, butylene glycol and its polyether diols, hexylene glycols and its polyether diols, butylene glycol and its polyether, hexylene diols glycol and its polyether diols, polyether diols synthesized by caprolactone ring opening polymerization, and urethane diols synthesized by the reaction of cyclic carbonates with diamines. The combination of these diols and polyether diols derived from combinations of various diols described above could also be used. Diol dimers can also be used including those sold under the trade name Pripol® and SolvermolTM, available from Cognis Corporation.
[0024] Polytetrahydrofuran-based polyols sold under the trade name Terathane®, including Terathane® 650, available from Invista, can be used. In addition, polyols based on diol dimers sold under the trade name Pripol® and Empol®, available from Cognis Corporation, or bio-based polyols, such as the tetrafunctional polyol Agrol 4.0, available from BioBased Technologies, can also be used.
[0025] Anhydride compounds useful for functionalizing the polyol with acid groups include hexahydrophthalic anhydride and its derivatives (for example, methyl hexahydrophthalic anhydride); phthalic anhydride and its derivatives (for example, methyl phthalic anhydride); maleic anhydride; succinic anhydride; trimethyl anhydride; pyromeletic dianhydride (PMDA); 3,3’-, 4,4’-oxidiftalic dianhydride (ODPA); 3,3’-, 4,4’-benzophenone tetracarboxylic dianhydride (BTDA); and 4,4'-diphthalic anhydride (hexamfluoroisopropylidene) (6FDA). The diacid compounds useful for functionalizing the polyol with acid groups include phthalic acid and its derivatives (for example, methyl phthalic acid), hexahydrophthalic acid and its derivatives (for example, methyl hexahydrophthalic acid), maleic acid, succinic acid, adipic acid, etc. . Any diacid and anhydride can be used; however, anhydrides are preferred.
[0026] In one embodiment, the polyol comprises a diol, the anhydride and / or diacid comprises a monoanhydride or a diacid, and the first epoxy compound comprises a diepoxy compound, where the molar ratio of diol, monoanhydride (or diacid), and Diepoxy compounds in the epoxy adduct can range from 0.5: 0.8: 1.0 to 0.5: 1.0: 6.0.
[0027] In another embodiment, the polyol comprises a diol, the anhydride and / or diacid comprises a monoanhydride or a diacid, and the first epoxy compound comprises a diepoxy compound, where the molar ratio of diol, monoanhydride (or a diacid) , and diepoxy compounds in the epoxy adduct can range from 0.5: 0.8: 0.6 to 0.5: 1.0: 6.0.
[0028] In another embodiment, the second epoxy compound of the first component is a diepoxide compound that has an epoxy equivalent weight between about 150 and about 1000. Suitable diepoxides having an epoxy equivalent weight between 150 and about 1000 include Bisphenol A polyglycidyl ethers, such as Epon® 828 and 10001 epoxy resins, and Bisphenol F diepoxides, such as Epon® 862, which are commercially available from Hexion Specialty Chemicals, Inc.
[0029] In another embodiment, the second epoxy compound of the first component is a diepoxide compound or a higher functional epoxide (collectively, a "polypoxide"), including polyhydric alcohol polyglycidyl ethers, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, and novolac epoxy resins.
[0030] In yet other non-limiting examples, the second epoxy compound includes epoxidated novolac bis, epoxidated phenolic novalacs, epoxidated cresyl novolac, and bismaleimide triglycidyl P-aminophenol.
[0031] In another embodiment, the second epoxy compound of the first component comprises an epoxy acid adduct. The epoxy acid dimer adduct can be formed as the reactant reaction product comprising a diepoxide compound (such as a Bisphenol A epoxy compound) and a dimer acid (such as a C36 dimer acid).
[0032] In another embodiment, the second epoxy compound of the first component comprises an epoxy compound modified by a carboxyl-terminated butadiene-acrylonitrile copolymer.
[0033] Useful amine compounds that can be used include primary amines, secondary amines, tertiary amines, and combinations thereof. Useful amine compounds that can be used include diamines, triamines, tetramines, and higher functional polyamines.
[0034] Suitable primary amines include alkyl diamines such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, neopentyldiamine, 1,8-diaminooctane, 1,10-diaminodecan, 1, -12-diaminododecan and the like; 1,5-diamino-3-oxapentane, diethylene triamine, triethylenetetramine, tetraethylenepentamine and the like; cycloaliphatic diamines such as 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornene and the like; aromatic alkyl diamines such as 1,3-bis (aminomethyl) benzene (m-xylene diamine) and 1,4-bis (aminomethyl) benzene (p-xylenediamine) and their reaction products with epichlorohydrin such as Gascamine 328 and the like; amine-terminated polyethylene glycol such as the Huntsman Corporation Jeffamine ED series and amine-terminated polypropylene glycol such as the Hunttsman Corporation Jeffamine D series; and amine-terminated polytetrahydrofuran such as the Huntsman Jeffamine E DR series. Primary amines having a functionality greater than 2 include, for example, the Jeffamine T series, available from Huntsman Corporation, which are amine or glycerol-terminated propoxylated trimethylolpropane and amine propoxylated pentaerythritols.
[0035] Other amines that can still be used include isophorone diamine, methenodiamine, 4,8-diamino-tricycle [5.2.1.0] decane and N-aminoethylpiperazine.
[0036] In certain embodiments, the amine compounds comprise triethylenetetramine (TETA), isophorone diamine, 1,3-bis (aminomethyl) cyclohexane, and polyetheramine based on polypropylene oxides.
[0037] In certain embodiments, polypropylene oxide-based polyetheramines comprise the Jeffamine series products available from Huntsman Chemical of Houston, Texas. The Jeffamina series products are polyetheramines characterized by the repetition of oxypropylene units in their respective structures.
[0038] An exemplary class of Jeffamina products, the so-called “Jeffamina D” series products, are PPGs terminated in amine (propylene glycol) with the following representative structure (Formula I):
where x is 2 to 70.
[0039] In certain embodiments, Jeffamina D-230 is a D series product that is used. Jeffamina D-230 has an average molecular weight of about 230 (where x is 2.5) and an equivalent hydrogen-amine (AHEW) weight of around 60. Other examples of Jeffamina D series products that can be used according to formula (I) include those where x is from 2.5 to 68.
[0040] Another series of polyethylene oxides based on polypropylene which are useful are predominantly tetrafunctional, primary amines with an average molecular weight number of 200 to 2000 and, more preferably, from 600 to 700, and having an AWEW greater than 60, and more preferably, 70 to 90. Jeffamine XTJ-616 is one of said polypropylene oxide-based polyetheramines that can be used in the present invention. Jeffamina XTJ-616 has an average molecular weight number of about 660 and an AHEW of 83.
[0041] The larger AHEW amine compounds, such as Jeffamina XTJ-616 and Jeffamina D-230, can be particularly useful in 2K adhesive compositions where a longer service life is desired. Conventional tetramines, such as triethylene tetramine, with smaller AWEWs have a substantially shorter shelf life in comparison. This invention thus provides a way to manipulate the life span with tetrafunctional amines such as Jeffamina XTJ-616.
[0042] In yet another embodiment, the reinforcing filler material can be added to the adhesive composition as a part of the first component or as a part of the second component, or both.
[0043] The payload reinforcing material that can be introduced into the adhesive composition to provide improved mechanical properties includes fibrous material, such as fiberglass, fibrous titanium dioxide, Whisker-type calcium carbonate (aragonite), and fiber carbon (which includes graphite and carbon nanotubes). In addition, fiberglass around 5 microns or greater and up to 50 microns or greater can also provide additional stress resistance. More preferably, fiberglass of about 5 microns or greater and 100-300 microns in length is used. Preferably, said reinforcement material, if used, comprises from 0.5 to 25 weight percent of the adhesive composition.
[0044] In yet another embodiment, filler, thixotropes, dyes, paints and other materials can be added to the first or second component of the adhesive composition.
[0045] Useful thixotropes that can be used include fumed silica (fumed silica) and treated fumed silica, Castor wax, clay, and organo clay. In addition, fibers such as synthetic fibers such as Aramid® and Kevlar® fiber, acrylic fibers, and constructed cellulose fibers can also be used.
[0046] Useful dyes or dyes may include red iron pigment, titanium dioxide, calcium carbonate, and phthalocyanine blue.
[0047] The payload material that can be used in conjunction with the thixotropes can include inorganic filler material such as inorganic clay or silica.
[0048] In yet another embodiment, if necessary, a catalyst can be introduced into the adhesive composition, preferably as a part of the second component, to promote the reaction of the epoxy groups of the first component and amine groups of the second component.
[0049] Useful catalysts that can be introduced into the adhesive composition include Ancamide® products available from Air Products and products marketed as “Accelerators” available from Huntsman Corporation (“Accelerators”). An example of a catalyst is Accelerator 399 based on piperazine (AHEW; 145) available from Huntsman Corporation. When used, said catalyst comprises between 0 and about 10 weight percent of the total adhesive composition.
[0050] In addition, a catalytic effect can be expected from the epichlorohydrin reaction product from the first component and from the amine compound from the second component in an equivalent ratio of 1: 1. An example of such a product is Tetrad® and Tetrad®C available from Mitsubishi Gas Chemical Corporation.
[0051] In certain embodiments, rubber particles having a core / shell structure can be included in the 2K structural adhesive formulation.
[0052] The appropriate core-shell rubber particles are comprised of butadiene rubber; however, other synthetic rubbers could be used, such as styrene-butadiene and acrylonitrile-butadiene and the like. The type of synthetic rubber and the concentration of the rubber should not limit the particle size within the specified ranges as illustrated below.
[0053] In certain embodiments, the average particle size of the rubber particles can be about 0.02 to 500 microns (20 mm at 500,000 nm).
[0054] In certain embodiments, the core / shell rubber particles are included in an epoxy carrier resin for introduction to the 2K adhesive composition, the appropriate finely dispersed core / shell rubber particles in an average particle size ranging from 50 nm to 250 nm are concentrated groups (“master-batched”) in epoxy aromatic epoxy resin, phenolic novolac epoxy resin, bisphenol A and bisphenol F and aliphatic epoxide, which include cycloaliphatic epoxides in concentrations ranging from 2 to 40 weight percent. Suitable epoxy resins can also include a mixture of epoxy resins.
[0055] Non-limiting examples of commercial core / shell rubber particle products using poly (butadiene) rubber particles having an average particle size of 100 nm that can be used in the 2K adhesive composition include a Kane Ace rubber dispersion MX 136 (a poly (butadiene core / shell) (25%) in Bisphenol F), Kane Ace rubber dispersion MX 153 (poly (butadiene core / shell) (33%) in Epon® 828), Kane Ace rubber dispersion MX 257 (a poly (butadiene) core-shell) (37%) in Bisphenol A), and Kane Ace rubber dispersion MX 267 (a poly (butadiene) core-shell) (37%) in Bisphenol F), each available from Kaneka Texas Corporation.
[0056] Non-limiting examples of core / shell rubber particle products using styrene-butadiene rubber particles having an average particle size of 100 nm that can be used in the 2K adhesive composition include Kane Ace MX 113 (a rubber dispersion of core / shell styrene-butadiene (33%) in low viscosity bisphenol A), Kane Ace MX 125 (a dispersion of core / shell styrene-butadiene rubber (25%) in bisphenol A), Kane Ace MX 215 (a dispersion of styrene-butadiene rubber core / shell (25%) in phenolic novolac epoxy DEN-438), and Kane Ace MX 416 (a dispersion of styrene-butadiene rubber core / shell (25%) in multi-functional epoxy MY -721), Kane Ace MX 451 (a dispersion of styrene-butadiene rubber core / shell (25%) in multi-functional epoxy MY-0510), Kane Ace MX 551 (a dispersion of core / shell styrene-butadiene rubber (25%) in cycloaliphatic epoxy Synasia 21), Kane Ace MX 715 (a dispersion of styrene-butadiene rubber and the core / shell (25%) in polypropylene glycol (MW 400)), each available from Kaneka Texas Corporation.
[0057] In certain embodiments, the amount of core / shell rubber particles included in the 2K adhesive formulation is 0.1 to 10 weight percent, such as 0.5 to 5 weight percent, based on weight total 2K coating composition.
[0058] In yet another embodiment, the graphene carbon particles can be included in the structural adhesive formulation 2K.
[0059] Graphene, as defined here, is an allotrope ("allotrope") of carbon, the structure of which is a 2-inch-thick planar blade of the carbon atoms attached to sp that are densely packed in a reticulated crystal of the type honeycomb. Graphene is stable, chemically inert and mechanically robust under ambient conditions. As used herein, the term "graphene carbon particles" means carbon particles having structures comprising one or more layers of planar layers of an atom thick of the carbon atoms attached to sp2 which are densely packed in a honeycomb-reticulated crystal. As such, the term “graphene carbon particles” includes a sheet with a thick layer (ie, graphene) and multi-layer thick sheets. The average number of layers stacked can be less than 100, for example, less than 50. In certain embodiments, the average number of packaged sheets is 30 or less. The graphene carbon particles can be substantially flat, however, at least a portion of the planar sheet can be substantially curved, wavy or tied. The particles typically do not have a spheroidal or solidized morphology of equiaxed forms (“equiaxed”).
[0060] In certain embodiments, the graphene carbon particles used in the present invention have a thickness, measured in a direction perpendicular to the carbon atom layers, of no more than 10 nanometers, such as no more than 5 nanometers or, in certain embodiments, no more than 3 or 1 nanometers. In certain embodiments, the graphene carbon particles can be from 1 atom layer to 10, 20 or 30 atoms thick in the layer, or more. Graphene particles can be provided in the form of ultrafine flakes, platelets or sheets having relatively high aspect ratios, greater than 3 :, such as greater than 10: 1.
[0061] In certain embodiments, the graphene carbon particles are milled by roll in an epoxy carrier resin, such as Epon® 828, to introduce the 2K adhesive layer. In an exemplary embodiment, a concentrated group (“master-batched”) of added epoxy resin / graphene carbon particles is formed by grinding the graphene carbon particles within the epoxy resin at a concentration of 10 percent or at a higher concentration . A dispersion method includes typical pigment crushing mills, such as three-roll mills, Eiger mills, Netsch / Premier mills and the like.
[0062] An example of graphene carbon particle material that can be used in the 2K adhesive formulation is Graphene Sciences XG Grade C, which has a surface area of 750 m2 / g, an average thickness of about 2 nano-meters , and an average diameter of less than 2 microns.
[0063] In certain embodiments, the amount of graphene carbon particles included in the 2K adhesive formulation is sufficient to provide the increased stress modulus while maintaining a glass transition temperature when compared to formulations not including graphene carbon particles.
[0064] In certain embodiments, the amount of graphene carbon particles included in the 2K adhesive formulation is about 0.5 to 25 weight percent based on the total weight of the 2K coating composition.
[0065] As also noted above, in certain embodiments, the 1K structural adhesives of the present invention comprise: (a) an epoxy-coated flexibilizer, and (b) a heat-activated latent curing agent. In certain embodiments, the 1K structural adhesives may additionally comprise one or more of the following components: (c) an epoxy / CTBN (a carboxy-terminated acrylonitrile butadiene polymer); (d) an epoxy acid / dimer adduct; (e) rubber particles having a core / shell structure; and (f) graphene carbon particles. Each component (a) - (e) is further described below.
[0066] In certain embodiments, the epoxy-capped flexibilizer is formed as the reactant reaction product comprising a first epoxy compound, a polyol, and an anhydride and / or a diacid (i.e., an anhydride, a diacid , or both, an anhydride and a diacid may be part of the reaction product).
[0067] Useful epoxy compounds that can be used include polyepoxides. Suitable polyepoxides include Bisphenol A polyglycidyl ethers, such as Epon® 828 and 1001 epoxy resins, and Bisphenol F diepoxide, such as Epon® 862, which are commercially available from Hexion Specialty Chemicals, Inc .. other useful polyepoxides include polyglycidyl ethers of polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, and novolac epoxy resins. Still other non-limiting examples of the first epoxy compound include epoxidated bisphenol A, epoxidated phenolic novalacs, epoxidated cresyl novolac, and bismaleiimide triglycidyl P-aminophenol.
[0068] Useful polyols that can be used include diols, triols, tetraols and higher functional polyols. The polyols can be based on a polyether chain derived from ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and the like, and mixtures thereof. The polyol can also be based on a polyester chain derived from the caprolactone ring opening polymerization. Suitable polyols may also include polyether polyol, polyurethane polyol, polybutadiene polyol, polycarbonate polyol, polysiloxane polyol, and combinations thereof. Polyamines corresponding to polyols can also be used, and in this case, amides instead of carboxylic esters will be formed with acids and anhydrides.
[0069] Suitable diols that can be used are diols having an equivalent hydroxyl weight between 30 and 1000. Examples of diols having an hydroxyl equivalent weight of 30 to 1000 include diols sold commercially under the trademark of Terathane®, including Terathane ® 250, available from Invista. Other examples of diols having a hydroxyl equivalent weight of 30 to 1000 include ethylene glycol and its polyether diols, propylene glycol and its polyether diols, butylene glycol and its polyether diols, hexylene glycols and its polyether diols, polyester diol synthesized by the opening polymerization of caprolactone and urethane diols synthesized by the reaction of cyclic carbonates with diamines. The combination of these diols and polyether diols derived from the various combinations of diols described above could also be used. Diol dimers can also be used including those sold under the trademark of Pripol® and SolvermolTM available from Cognis Corporation.
[0070] Polytols based on polytetrahydrofuran sold under the trademark Terathane®, including Terathane® 650, available from Invista, can be used. In addition, polyols based on diol dimers sold under the trademark Pripol® and Empol®, are available from Cognis Corporation, or bio- based polyols, such as tetrafunctional polyol AGrol 4.0, available from BioBased Technologies, can also be used.
[0071] Anhydride compounds useful for functionalizing the polyol with acid groups include hexahydrophthalic anhydride and its derivatives (for example, methyl hexahydrophthalic anhydride); phthalic anhydride and its derivatives (for example, methyl phthalic anhydride); maleic anhydride; succinic anhydride; trimethyl anhydride; pyromeletic dianhydride (PMDA); 3,3’-, 4,4’-oxyphthalic dianhydride (ODPA); 3,3'-, 4,4’-tetracarboxylic dianhydride (BTDA); and 4,4'-diphthalic anhydride (hexamfluoroisopropylidene) (6FDA). The diacid compounds useful for functionalizing the polyol with acid groups include phthalic acid and its derivatives (for example, methyl phthalic acid), hexahydrophthalic acid and its derivatives (for example, methyl hexahydrophthalic acid), maleic acid, succinic acid, adipic acid, etc. . Any diacid and anhydride can be used; however, anhydrides are preferred.
[0072] In one embodiment, the polyol comprises a diol, the anhydride and / or diacid comprises a monoanhydride or a diacid, and the first epoxy compound comprises a diepoxy compound, where the molar ratio of diol, monoanhydride (or diacid), and Diepoxy compounds in the epoxy capped flexibilizer can vary from 0.5: 0.8: 1.0 to 0.5: 1.0: 6.0.
[0073] In another embodiment, the polyol comprises a diol, the anhydride and / or diacid comprises a monoanhydride or a diacid, and the first epoxy compound comprises a diepoxy compound, where the molar ratio of diol, monoanhydride (or a diacid) , and diepoxy compounds in the epoxy capped flexibilizer can vary from 0.5: 0.8: 0.6 to 0.5: 1.0: 6.0.
[0074] In certain embodiments, the epoxy-capped flexibilizer comprises the reagent reaction product comprising an epoxy compound, an anhydride and / or a diacid, and a caprolactone. In certain other embodiments, a diamine and / or a higher functional amine can also be included in the reaction product in addition to the epoxy compound, caprolactone, and the anhydride and / or a diacid.
[0075] Suitable epoxy compounds that can be used to form the epoxy capped flexibilizer include functional epoxy polymers that can be saturated or unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic. Epoxy-functional polymers can have pendant or terminal hydroxyl groups, if desired. They can contain substituents such as halogen, hydroxyl, and ether groups. A useful class of these materials includes polyepoxides comprising epoxy polyethers obtained by reacting an epihalohydrin (such as epichlorohydrin or epibromohydrin) with a di- or polyhydric alcohol in the presence of an alkali. Suitable polyhydric alcohols include polyphenols such as resorcinol; catechol; hydroquinone: bis (4-hydroxyphenyl) -2,2-propane, that is, bisphenol A; bis (4-hydroxyphenyl) -1,1-isobutane; 4,4-dihydroxybenzophenone; bis (4-hydroxyphenol) -1,1-ethane; bis (2-hydroxyphenyl) -methane and 1,5-hydroxynaphthalene.
[0076] Commonly used polyepoxides include Bisphenol A polyglycidyl ethers, such as Epon® 828 epoxy resin which is commercially available from Hexion Specialty Chemicals, Inc., and has an average molecular weight number of about 400 and an equivalent weight of epoxy from about 185-192. Other useful polyepoxides include polyglycidyl ethers of other polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, which are partially oxidized and novelized by polyacrylic resins. carboxylic acids, alcohol, water, phenols, mercaptan or other compounds containing active hydrogen to result in hydroxyl-containing polymers.
[0077] Useful anhydride compounds that can be used include hexahydrophthalic anhydride and its derivatives (for example, hexahydrophthalic methyl anhydride); phthalic anhydride and its derivatives (for example, methyl phthalic anhydride); maleic anhydride; succinic anhydride; trimelletic anhydride; pyromeletic dianhydride (PMDA); 3,3'- 4,4'-oxidiftalic dianhydride (ODPA); 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA); and 4,4'-diphthalic anhydride (hexamfluoroisopropylidene) (6FDA). The diacid compounds useful for functionalizing the polyol with the acid groups include phthalic acid and its derivatives (for example, methyl phthalic acid), hexahydrophthalic acid and its derivatives (for example, hexahydrophthalic methyl acid), maleic acid, succinic acid, adipic acid, etc. any diacid and anhydride can be used; however, anhydrides are preferred.
[0078] Useful caprolactones that can be used include caprolactone monomers, caprolactone monomers replaced with methyl, ethyl, and propyl, and polyester diols derived from caprolactone monomers. Examples of polyester diols having a molecular weight of about 400 to 8000 include diols sold under the trade name CAPA®, including CAPA® 2085, available from Perstorp.
[0079] Useful diamine or higher functional amine compounds that can be used to form the epoxy capped flexibilizer include primary amines, secondary amines, tertiary amines, and combinations thereof. Useful amine compounds that can be used include diamines, triamines, tetramines, and higher functional polyamines.
[0080] Suitable primary diamines or higher functional amines that can be used include alkyl diamines such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, neopentyldiamine, 1,8-diaminooctane, 1,10- diaminodecane, 1, -12-diaminododecane and the like; 1,5-diamino-3-oxapentane, diethylene-triamine, triethylenetetramine, tetraethylenepentamine and the like; cycloaliphatic diamines such as 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl0cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (aminomethyl) norbornene and the like; alkyl aromatic diamines such as 1,3-bis ( aminomethylbenzene (m-xylene diamine) and 1,4-bis (aminomethyl) benzene (p-xylenediamine) and their reaction products with epichlorohydrin such as Gascamine 328 and the like; amine-terminated polyethylene glycol such as Jeffamine ED series from Huntsman Corporation; and amine-terminated polypropylene glycol such as Huntsman Corporation's Jeffamine D series, and amine-terminated polytetrahydrofuran such as Huntsman's EDR series Jeffries. Primary amines having a functionality greater than 2 include, for example, the Jeffamine T series, available from Huntsman Corporation, which are propoxylated amine or glycerol trimethylolpropane and propoxylated amino pentaerythritol.
[0081] In certain embodiments, polypropylene oxide-based polyesteramines comprise the Jeffamine series products available from Huntsman Chemical of Houston, Texas. The Jeffamine series products are polyesteramines characterized by the repetition of oxypropylene units in their respective structures.
[0082] An exemplary class of Jeffamine products, the so-called “Jeffamine D series products”, are PPGs terminated in amines (propylene glycol) with the following representative structure (Formula (I)):
(I) where x is 2 to 70.
[0083] In one embodiment, caprolactone comprises a caprolactone monomer, the anhydride and / or diacid comprises a monoanhydride or a diacid, and the first epoxy compound comprises a diepoxy compound, where the molar ratio of caprolactone monomer, monoanhydride (or diacid), and the epoxy compounds in the epoxy capped flexibilizer can range from 0.5: 0.8: 1.0 to 0.5: 1.0: 6.0.
[0084] In one embodiment, caprolactone comprises a caprolactone monomer, the anhydride and / or diacid comprises a monoanhydride or a diacid, and the first epoxy compound comprises a diepoxy compound, where the molar ratio of caprolactone monomer, monoanhydride (or diacid), and the epoxy compounds in the epoxy capped flexibilizer can range from 0.5: 0.8: 0.6 to 0.5: 1.0: 6.0.
[0085] In one embodiment, caprolactone comprises a caprolactone monomer, the anhydride and / or diacid comprises a monoanhydride or a diacid, the top functional diamine or amine comprises a diamine, and the first epoxy compound comprises a diepoxy compound, where the molar ratio of caprolactone monomer, monoanhydride (or diacid), diamine and diepox compounds in the epoxy capped flexibilizer can vary from 2: 1: 2: 2 to 3: 1: 3: 3.
[0086] In certain embodiments, the epoxy-capped flexibilizer comprises the reagent reaction product comprising an epoxy compound and a primary amine or secondary polyether amine.
[0087] Suitable epoxy compounds that can be used to form the epoxy capped flexibilizer include functional epoxy polymers that can be saturated or unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic. Functional epoxy polymers can have pendant or terminal hydroxyl groups, if desired. They can contain substituents such as halogen, hydroxyl, and ether groups. A useful class of these materials includes polyepoxides comprising epoxy polyethers obtained by reacting an epihalohydrin (such as epichlorohydrin or epibromohydrin) with a di- or polyhydric alcohol in the presence of an alkali. Suitable polyhydric alcohols include polyphenols such as resorcinol; catechol; hydroquinone: bis (4-hydroxyphenyl) -2,2-propane, that is, bisphenol A; bis (4-hydroxyphenyl) -1,1-isobutane; 4,4-dihydroxybenzophenone; bis (4-hydroxyphenol) -1,1-ethane; bis (2-hydroxyphenyl) -methane and 1,5-hydroxynaphthalene.
[0088] Poliepoxides frequently used include Bisphenol A polyglycidyl ethers, such as Epon® 828 epoxy resin which is commercially available from Hexion Specialty Chemicals, Inc., and has an average molecular weight of about 400 and an equivalent weight of epoxy from about 185-192. Other useful polyepoxides include polyglycidyl ethers of other polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, which are partially polyacethoxylated and resoluted by polyacrylic resins. carboxylic acids, alcohol, water, phenols, mercaptan or other compounds containing active hydrogen to result in hydroxyl-containing polymers.
[0089] Primary and secondary polyether amine compounds that can be used to form an epoxy-capped flexibilizer include amine-terminated polyethylene glycol such as Jeffamine Huntsman Corporation's ED series and amine-terminated propylene glycol, such as Huntsman's Jeffamine D series Corporation; and amine-terminated polytetrahydrofuran such as Huntsman's Jeffamine EDR series. Primary amines having a functionality greater than 2 include, for example, Jeffamine T series, available from Huntsman Corporation, which are amine or glycerol-terminated propoxylated trimethylolpropane and propoxylated amino pentaerythritol.
[0090] In one embodiment, the epoxy compound comprises a diepoxide, and the secondary primary polyether amine comprises a difunctional amine, where the molar ratio of diepoxide to difunctional amine ranges from 2: 0.1 to 2: 1.
[0091] In certain embodiments, the 1K structure adhesive may include 2 to 40 weight percent, such as 10 to 20 weight percent of (a) epoxy capped flexibilizer, based on the total weight of the structural adhesive composition 1K, in any of the ways described above.
[0092] In yet other related embodiments, the epoxy capped flexibilizer may comprise a mixture of any two or more epoxy capped flexibilizers described above, where the weight percentage of two or more of the epoxy capped flexibilizers comprises of 2 to 40 weight percent, such as 10 to 20 weight percent of the structural adhesive composition 1K.
[0093] In certain embodiments, the heat activated latent curing agent that can be used includes guanidines, substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, cyclic tertiary amines, aromatic amines and / or mixtures thereof. Hardeners can be involved stoichiometrically in the hardening reaction; they can, however, also be catalytically active. Examples of substituted guanidines are methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, methylisobiguanidine, dimethylisobiguanidine, tetramethylisobiguanidine, hexamethylisobiguanidine, heptamethylisobigidanidine and especially dichuanydine, and more. Representatives of suitable guanamine derivatives that can be mentioned are alkylated benzoguanamine resins, benzoguanamine resins or methoxymethylethoxymethylbenzoguanamine. In addition, catalytically active substituted ureas can also be used. Catalytically active substituted ureas include p-chlorophenyl-N, N-dimethylurea, 3-phenyl-1,1-dimethylurea (phenuron) or 3,4-dichlorophenyl-N, N-dimethylurea.
[0094] In certain other embodiments, the heat-activated latent curing agent also or alternatively comprises dicyandiamide and 3,4-dichlorophenyl-N, N-dimethylurea (also known as Diuron).
[0095] In certain embodiments, the 1K structure adhesive may include 3 to 25 weight percent, such as 5 to 10 weight percent of (b) the heat activated latent curing agent, based on the total weight of the adhesive composition 1K structure.
[0096] As noted above, in certain embodiments, the 1K structural adhesive composition may include (c) an epoxy / CTBN adduct. In certain embodiments, the liquid polymer CTBN passes through the addition of esterification reactions with epoxy resins, allowing them to serve as elastomeric modifiers to improve impact resistance, resistance to flaking, and crack resistance.
[0097] Suitable epoxy compounds that can be used to form the epoxy / CTBN adduct include epoxy-functional polymers that can be saturated or unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic. Epoxy-functional polymers can have pendant or terminal hydroxyl groups, if desired. They can contain substituents such as halogen, hydroxyl, and ether groups. A useful class of these materials includes polyepoxides comprising epoxy polyethers obtained by reacting an epihalohydrin (such as epichlorohydrin or epibromohydrin) with a di- or polyhydric alcohol in the presence of an alkali. Suitable polyhydric alcohols include polyphenols such as resorcinol; catechol; hydroquinone: bis (4-hydroxyphenyl) -2,2-propane, that is, bisphenol A; bis (4-hydroxyphenyl) -1,1-isobutane; 4,4-dihydroxybenzophenone; bis (4-hydroxyphenol) -1,1-ethane; bis (2-hydroxyphenyl) -methane and 1,5-hydroxynaphthalene.
[0098] Commonly used polyepoxides include Bisphenol A polyglycidyl ethers, such as Epon® 828 epoxy resin which is commercially available from Hexion Specialty Chemicals, Inc., and has an average molecular weight of about 400 and an equivalent weight of epoxy from about 185-192. Other useful polyepoxides include polyglycidyl ethers of other polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, which are partially oxidized and novelized by polyacrylic resins. carboxylic acids, alcohol, water, phenols, mercaptan or other compounds containing active hydrogen to result in hydroxyl-containing polymers.
[0099] In certain embodiments, at least a portion, often at least 5 percent weighted, of the polyepoxides has been reacted with a carboxy-terminated acrylonitrile butadiene polymer. In certain embodiments, the carboxy-terminated acrylonitrile butadiene polymers have an acrylonitrile content of 10 to 26 weight percent. Suitable CTBN compounds having a 10 to 26 percent weight acrylonitrile content that can be used include Hypro 1300X8, Hypro 1300X9, Hypro 1300X13, Hypro 1300X18, and Hypro 1300X31, each available from Emerald Specialty Polymers, LLC of Akron, Ohio.
[0100] In other certain embodiments, the polyepoxides can be reacted with a mixture of different carboxy-terminated acrylonitrile butadiene polymers.
[0101] In certain embodiments, the functionality of the CTBN used is 1.6 to 2.4, and the epoxy compound is reacted with the CTBN material in a stoichiometric amount to form the epoxy / CTBN adduct.
[0102] In certain embodiments, the epoxy / CTBN adduct comprises from about 1 to 20 weight percent, as well as from 5 to 10 weight percent, of the total weight of the 1K structural adhesive composition.
[0103] As noted above, in certain embodiments, the 1K structural adhesive composition may include (d) an epoxy / dimer acid adduct. In certain embodiments, the epoxy / dimer acid adduct can be formed by reacting an epoxy compound with a dimer acid.
[0104] Suitable epoxy compounds that can be used to form the epoxy acid / dimer adduct include functional epoxy polymers that can be saturated or unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic. Epoxy-functional polymers can have pendant or terminal hydroxyl groups, if desired. They can contain substituents such as halogen, hydroxyl, and ether groups. A useful class of these materials includes polyepoxides comprising epoxy polyethers obtained by reacting epihalohydrins (such as epichlorohydrin or epibromohydrin) with a di- or polyhydric alcohol in the presence of an alkali. Suitable polyhydric alcohols include polyphenols such as resorcinol; catechol; hydroquinone: bis (4-hydroxyphenyl) -2,2-propane, that is, bisphenol A; bis (4-hydroxyphenyl) -1,1-isobutane; 4,4-dihydroxybenzophenone; bis (4-hydroxyphenol) -1,1-ethane; bis (2-hydroxyphenyl) -methane and 1,5-hydroxynaphthalene.
[0105] Commonly used polyepoxides include Bisphenol A polyglycidyl ethers, such as Epon® 828 epoxy resin which is commercially available from Hexion Specialty Chemicals, Inc., and has an average molecular weight of about 400 and an equivalent weight of epoxy from about 185-192. Other useful polyepoxides include polyglycidyl ethers of other polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, which are partially oxidized and novelized by polyacrylic resins. carboxylic acids, alcohol, water, phenols, mercaptan or other compounds containing active hydrogen to result in hydroxyl-containing polymers.
[0106] As defined here, dimer acids, or dimerized fatty acids, are dicarboxylic acids prepared by dimerizing unsaturated fatty acids obtained from tall oil, usually over clay catalysts. Dimer acids contain predominantly a stearic acid dimer known as C36 dimer acid. A dimer acid suitable for use in forming the epoxy acid / dimer adduct of the present invention can be obtained from Croda, Inca., Or Cognis.
[0107] In certain embodiments, the epoxy compounds and dimer acids are reacted in stoichiometric amounts to form the epoxy acid / dimer adduct.
[0108] In certain embodiments, the epoxy acid / dimer adduct comprises about 1 to 15 weight percent, as well as 2 to 7 weight percent, of the total weight of the 1K structure adhesive composition.
[0109] As noted above, in certain embodiments, the 1K structural adhesive composition may also include (e) rubber particles having a core / shell structure. The core / shell rubber particles suitable for use in 1K structural adhesives are the same as those described above with respect to 2K adhesive formulations and are therefore not repeated here.
[0110] In certain embodiments, the 1K structural adhesive may include 0 to 75 percent, such as 5 to 60 percent weight, of (e) rubber particles having a core / shell structure, based on the total weight of the structural adhesive composition of 1K.
[0111] As noted above, in certain embodiments, the structural adhesive composition of 1K may also include (f) graphene carbon particles. The graphene carbon particles suitable for use in 1K structural adhesives are the same as those described above with respect to 2K adhesive formulations and therefore will not be repeated here.
[0112] In certain embodiments, the 1K structural adhesive may include 0 to 40 weight percent, such as 0.5 to 25 weight percent, of (f) graphene carbon particles, based on the total weight of the structural adhesive composition of 1K.
[0113] In still other embodiments, the structural adhesive formulation 1K may also include epoxy compounds or resins that are not incorporated into or reacted as a part of any of the components (a) - (f) above, including functional epoxy polymers that can be saturated or unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic. Epoxy-functional polymers can have pendant or terminal hydroxyl groups, if desired. They can contain substituents such as halogen, hydroxyl, and ether groups. A useful class of these materials includes polyepoxides comprising epoxy polyethers obtained by reacting an epihalohydrin (such as epichlorohydrin or epibromohydrin) with a di- or polyhydric alcohol in the presence of an alkali. Suitable polyhydric alcohols include polyphenols such as resorcinol; catechol; hydroquinone: bis (4-hydroxyphenyl) -2,2-propane, that is, bisphenol A; bis (4-hydroxyphenyl) -1,1-isobutane; 4,4-dihydroxybenzophenone; bis (4-hydroxyphenol) -1,1-ethane; bis (2-hydroxyphenyl) -methane and 1,5-hydroxynaphthalene.
[0114] Commonly used polyepoxides include Bisphenol A polyglycidyl ethers, such as Epon® 828 epoxy resin which is commercially available from Hexion Specialty Chemicals, Inc., and has an average molecular weight of about 400 and an equivalent weight of epoxy from about 185-192. Other useful polyepoxides include polyglycidyl ethers of other polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, which are partially oxidized and novelized by polyacrylic resins. carboxylic acids, alcohol, water, phenols, mercaptan or other compounds containing active hydrogen to result in hydroxyl-containing polymers.
[0115] In yet another embodiment, the reinforcing filler material can be added to the adhesive composition. Useful reinforcing filler materials that can be introduced into the adhesive composition to provide improved mechanical properties include fibrous materials, such as fiberglass, fibrous titanium dioxide, Whisker-type calcium carbonate (aragonite), and carbon fiber (which includes graphite and carbon nanotubes). In addition, fiberglass around 5 microns or greater and up to 50 microns or greater can also provide additional stress resistance. More preferably, fiberglass of about 5 microns or greater and 100-300 microns in length is used. Preferably, said reinforcement material, if used, comprises from 0.5 to 25 weight percent of the adhesive composition.
[0116] In yet another embodiment, filler material, thixotropes, dyes, paints and other materials can be added to the 1K adhesive composition.
[0117] Useful thixotropes that can be used include fumed silica (fumed silica) and treated fumed silica, Castor wax, clay, and organo clay. In addition, fibers such as synthetic fibers such as Aramid® and Kevlar® fiber, acrylic fibers, and constructed cellulose fibers can also be used.
[0118] Useful dyes or inks can include red iron pigment, titanium dioxide, calcium carbonate, and phthalocyanine blue.
[0119] The payload material that can be used in conjunction with the thixotropes can include inorganic filler material such as inorganic clay or silica.
[0120] Examples of other materials that can be used include, for example, calcium oxide and carbon black.
[0121] To illustrate the invention, examples are given below which should not be considered as limiting the invention in its details. All parts and percentages in the examples, as well as in the entire specification, are given by weight unless otherwise indicated. EXAMPLES Example 1 - 2K adhesive compositions: Part A - Synthesis of polyether polyester modified epoxy resin:
[0122] In a four-necked flask fitted with a condenser, thermometer, stirrer and nitrogen inlet, 304.6 grams of hexahydrophthalic anhydride and 248.1 grams of Terathane® 250 were added. Heat the mixture to 100 ° C with stirring under a nitrogen atmosphere and maintaining the reaction mixture at 100 ° C for 155 minutes. Cool the reaction mixture to 60 ° C and then add 1431.6 grams of Epon® 828 and 15.0 grams of triphenyl phosphine. Heat the reaction mixture to 110 ° C and keep at this temperature for 150 minutes. Then, cool the mixture to room temperature. The resulting compound has 99.89% solids, an acid value of 0.2, and an epoxy equivalent weight of 380.7. The resulting compound is the epoxy adduct of the first component of the 2K adhesive material listed in part 1 of table 1 below. Part B - Evaluation of 2K adhesives with and without epoxy adduct; Evaluation of 2K adhesives with variation in the equivalent weight of amine-hydroxyl
[0123] The following examples compare 1K adhesive compositions without an epoxy adduct (Example 1) to those with an epoxy adduct (Examples 2-4). The formulations for the first component (Part 1) and the second component (Part 2) of the 2K adhesive compositions are shown in Table 1. Table 1
1. Bisphenol A / Epichlorohydrin resin available from Huntsman Advance Materials; 2. Example of synthesis from Example 1, Part A; 3. Fibertec chopped glass fiber treated silane; 4. Carbonatod and precipitated calcium available from Shiraishi Kogyo Kaisha; 5. Hydrophobic fumed silica available from Wacker Ghemie Ag; 6. Yellow ORG paint base available from Elementis Specialties; 7. Polyoxyalkyleneamine available from Huntsman; 8. Polyoxyalkyleneamine available from Huntsman; 9. Triethylenetetramine available from Dow Chemical Co .; 10. Isoforn diamine available from Evonik AG; 11. Mixture of alkanolamine / piperazine derivatives available from Huntsman; 12. Phthalan blue pigment dispersion, available from Elementis Specialtis. Test Method:
[0124] In each of the Examples, the raw materials listed in Table 1 were mixed using a DAC 600 FVZ speed mixer (“Speedmixer”) (commercially available from FlackTek, Inc.). Ingredients 1 and 2 were mixed for 2 minutes at 2350 revolutions per minute ("RPM") in Part 1. Then, items 3 to 6 were added and mixed for one minute at 2350 rpm. Items 7 to 11 were mixed for 1 minute in Part 2 and then the rest of the ingredients were added and mixed for one minute in Part 2. During the mixing process, the mixture was examined with a spatula and given additional mixing time , if necessary, to ensure uniformity. The final step of the mixing process involves mixing the mixture with an air motor support in a vacuum sealed apparatus for 5 minutes at 28 to 30 inches of vacuum pressure. After the final mixing step, with the air motor support, the adhesive compositions were ready for testing.
[0125] Part 1 and Part 2 were targets for 2: 1 volume mixing ratio. In some examples, the appropriate weight ratios have been determined to test the properties. The ratio of amine to epoxy was kept slightly above one for all examples to ensure the complete reaction of epoxy as shown in the result section of Table 1. The appropriate weight ratio of part 1 and part 2 were weighed and mixed in the mixer DAC for one minute at 2350 RPM and mixed immediately under vacuum as described in the previous paragraphs. The mixed sample was then subjected to the following tests:
[0126] Lap Shear Test: 25 mm x 100 mm coupons were cut from 6-ply unidirectional glass / epoxy laminates (“6-ply”) provided by MFG, Inc., with peel fold removal. The coupons were delimited on one side by 12.5 mm. The adhesive was applied uniformly to one of the coupons within the defined area for each connection arrangement. The uniformity of the connection thickness was guaranteed by the addition of 1.0 + 0.5 mm glass spacer beads. The spacer beads were sprinkled evenly over the material, covering no more than 5% of the total bonding area. The other test coupon was placed over a connection area and spring-loaded clips, such as the Office Max binder clips or Home Depot mini-clips, were attached, one on each side of the connection, to retain the arrangement together during cooking. Care was taken to align the parallel edges. The excess adhesive that was compressed was removed with a spatula before cooking. The binding arrangements were given in an open time of 15 to 30 minutes and cooked at 70 ° C for six hours, and after cooling, the remaining excess was sanded. The connections were conditioned at room temperature for at least 24 hours. The connection was inserted into wedging clips and pulled at a rate of 10 mm per minute using an Instron 5567 Model in tension mode. Lap shear strength was calculated using the Instron’s Blue Hill software package.
[0127] Mechanical properties of the free film: the same adhesive mixture was used to prepare films in the form of dog bone free of voids through the trimming material with care to avoid any air bubble. Figure 1 is an example of a Teflon mold for making five dog bone cavities. The mold was glued to a solid piece of Teflon with double-sided adhesive tape before the chip adhesive in the cavity. This arrangement was done in an open-air time of 15 to 30 minutes and then cooked at 70 ° C for 6 hours. It was packed for at least 24 hours, and then the dog bone film was blown out of the mold. The current thickness and width were recorded in the Instron 5567 software. Then, the dog bone was inserted into the clamp with chock action and dragged at a rate of 50 mm per minute. The percentage of elongation, tensile strength, and modulus were determined with the Instron’s Blue Hill software package. Alternatively, The ISO 527-1 & 2 method, and the mold configuration was used when indicated in the tables to prepare the free-form film of dog bone (halter - “dumb-bell”).
[0128] The controlled load lap shear fatigue test was done using the same laminate and coupon construction as described in the previous paragraph. An automated system using instron servo-controlled, hydraulically actuated, closed-loop test equipment and a personal computer with software designated by Westmoreland, Inc. Mechanical Testing and Research (“Westmoreland Mehanical Testing and Research, Inc.”), providing the means for controlling the machine. Each species was inserted into the clamp with shim action together with a frictional retained metal plate with a thickness equal to that of the fiberglass substrates and the connecting line to guarantee the axial load. The test was carried out at room temperature with a ratio of R from 0.1 to 5 Hz in the form of a sine wave and the application of a load of 8 MPa. The test was continued until 432,000 cycles or until failure. Part C - Life assessment with 2K adhesive having equivalent weights of hydroxy amine variant:
[0129] Table 2 shows the comparison of the useful life between propylene oxide-based polyether tetramines, Jeffamine XTJ-616, and ethylene oxide-based triethylene tetramine in similar formulas, where the amine / epoxy ratio was maintained between 1 , 02 and 1.05. The formulations and results are shown in Table 2.

[0130] In this experiment, both formulas (examples 5 and 6) used in the same quantity as the Accelerator 399, which also has a significant influence on the service life. If the Accelerator 399 was absent, the service life was observed to be significantly longer.
[0131] The service life has been defined as the time interval when Part 1 (the epoxy component) and Part 2 (the amine component) are mixed for a time when the internal temperature of the adhesive reaches 50 ° C in 415 ml of pasta. Part 1 and part 2 were mixed in a 2 to 2 volume ratio using a static mixer; double pneumatic PC COX applicator dispensing the mixed adhesive in a paper cup sold with 415 ml. The level line and the initial time were observed. The cup was immediately placed in a 25 ° C water bath with a thermo coupler inserted in the center of the mixed adhesive mass. The PC-based data logging device was used to record the temperature every minute to determine the useful life to reach 50 ° C, the peak temperature, and the time to reach the peak temperature. PART D - Evaluation of 2K adhesives with and without reinforcement load material:
[0132] In this experiment, the effect of adding glass fiber as a reinforcement material was compared in a sample formulation as described in table 3.
[0133] Examples 7 and 8 in Table 3 are a comparative study with and without Microglass 9132 (fiberglass strips with an average of 220 microns in length). The results indicate a significant increase in the module, when Microglass 9132 is present.
PART E - evaluation of 2K adhesives with graphene carbon particles: evaluation of 2K adhesive systems with rubber particles having a core / shell structure:
[0134] The following examples compare 2K adhesive compositions with graphene carbon particles (Example 2) or with rubber particles having a core / shell structure (Example 3). The formulations for the first component (Part 1) and the second component (Part 2) of the 2K adhesive compositions are shown in Table 4.
[0135] In the examples using the graphene carbon particles, twenty grams of xGnP® graphene nanoplank (Grade C in the surface area of 750 m2 / g (available from SG Sciences Corporation) was added to the pre-weighed Epon® 828 (180 grams available from Hexion Specialty Chemicals Corporation) and the mixture was manually mixed with a spatula in a laboratory glove box, the mixture was then poured into a three-roll mill (manufactured by Kent Industrial USA Inc) and ground 6 times. ® ground graphene was poured from the mill and introduced to the mixture as in Example 2 below.
13. Epon® 828 / Terathanne 650 / Hexahydrophthalic anhydride adduct; EEW 412; 14. Available from XG Sciences, dispersion of graphene carbon particles (10%) in Epon® 828 15. Poly (butadiene) core / shell rubber dispersion in Epon®828, available from Kaneka Texas Corporation; 16. polyoxyalkyleneenoamine, available from Huntsman 17. 1,3-bis (aminomethyl0cyclohexane (1,3-BAC), available from Mitsubishi Gas Chemical. EXAMPLE 2 - 1K adhesive compositions: PART A - Synthesis of Polyether-polyester modified epoxy resin
[0136] In a four-necked flask fitted with a condenser, thermometer, shaker, and nitrogen inlet, 321.3 grams of hexahydrophthalic anhydride and 677.7 grams of Terathane® 650 were added. The mixture was heated to 100 ° C with stirring under a nitrogen atmosphere and the reaction was verified for an exotherm. After the exotherm decreased, the temperature was adjusted to 150 ° C and maintained until the anhydride peak at 1785 and 1855 CM-1 disappeared. The reaction mixture was then cooled to 120 ° C, where 1646.0 grams of EPON 828 and 15.0 grams of triphenyl phosphine were added. The reaction mixture was maintained at 120 ° C until the acid value was below 2.2, resulting in a polyether-polyester modified epoxy resin having an epoxy equivalent weight of 412. PART B - Synthesis of polycaprolactone modified epoxy resin diol:
[0137] To an appropriate flask equipped with a reflux condenser and a shaker, 211.9 grams of hexahydrophthalic anhydride and 570.6 grams of CAPA 2085 polycaprolactone were added. The mixture was heated to 100 ° C while stirring and maintained if until the acid value is below 125 and the IR anhydride peak in 1785 to 1855 CM-1 disappears. The reaction mixture was then cooled to room temperature and 221 grams of this derivative was added to another flask equipped with a reflux condenser and stirrer. 310.6 grams of Epon® 828 (Bisphenol A - epichlorohydrin) and 3.00 grams of triphenylphosphine were added to the derivative, and the mixture was heated to 110 ° C while stirring. The heating mat was removed when the exotherm temperature increased by about 145 ° C to allow the temperature to decrease. The reaction temperature was then maintained at about 110 ° C until the acid value of the mixture was below 2. The reaction mixture was then cooled to room temperature and stored. The resulting polycaprolactone diol modified epoxy resin had an average molecular weight (Mn) of 2042 and an epoxy equivalent weight (EEW) of 435. PART C - Synthesis of the amide-polyether-polyester modified epoxy resin:
[0138] 323.5 grams of Jeffamine D400 and 167.6 grams of E-caprolactone was added in an appropriate flask equipped with a reflux condenser and shaker. The mixture was heated to 150 ° C while stirring until the MEQ amine value was below 0.75 MEQ / gm. The mixture was then cooled to 60 ° C, where 1061.8 grams of Epon® 828 and 3.7 grams of triphenylphosphine were added. The mixture was then heated to 110 ° C while stirring and maintained at that temperature until the acid value was below 2. The mixture was then cooled to room temperature and stored. The resulting amide-polyether-polyester modified epoxy resin had an average molecular weight of 1664 and an epoxy equivalent weight (EEW) was 408.6. PART D - Synthesis of epoxy acid / dimer adducts:
[0139] Empol® 1022 dimer acid (26.95 grams, available from Emory), Epon® 828 (32.96 grams available from Hexion) and triphenylphosphine (0.06 grams, available from BASF) were added in a vial of round bottom, which was equipped with a mechanical stirrer, a reflux condenser. A thermometer and an addition funnel were connected. The nitrogen gas was briefly introduced into the flask. The flask was heated to 105 ° C and the reaction continued until the acid value reached the desired range between 85 to 88 mg KOH per gram. An additional amount of Epon® 828 (40.03 grams) was added to the flask through a 105 ° C funnel and nitrogen gas was briefly introduced into the flask. The flask was heated to 116 ° C. A medium exotherm reaction takes place and the reaction temperature reaches 177 ° C. The flask temperature was returned to and kept under 168 ° C by cooling. The reaction continued until the acid value became less than 1, where the flask was cooled to room temperature. This synthesis caused 43.6% of the epoxy acid / dimer adduct to disperse in an epoxy resin having an epoxy equivalent weight (EEW) of 338.6. PART E - Synthesis of epoxy adduct / CTBN:
[0140] Butadiene finished in HYCAR 1300X8 carboxylic acid - acrylonitrile rubber (40 grams, available from Emerald Performance Materials Corporation) and Epon® 828 (60 grams) were added in a round bottom flask, equipped with a mechanical stirrer, a thermometer and a reflux condenser. The flask was heated to 115 ° C under a nitrogen atmosphere. The mixture was then heated to 165 ° C and stirred at that temperature until the acid value became less than 0.1, where the flask was cooled to room temperature. This synthesis caused 43.6% of the epoxy acid / dimer adduct to disperse in an epoxy resin having an epoxy equivalent weight (EEW) of 338.6. PART F - Synthesis of polyetheramine modified epoxy resin:
[0141] 187 grams of Epon® 828 were added to a metal can and heated in an oven at 95 ° C for 30 minutes. The can was removed from the oven and was adjusted with a mechanical stirrer driven with an air motor with blades surrounded by a high shear mixture. 38.33 grams of Jeffamina D-400 was gradually added to the can under high speed mixing, and the mixture was stirred for three hours. During this period, the temperature of the mixture, initially at about 120 ° C (as measured in a thermocouple), was gradually decreased. After three hours, the can was cooled to room temperature. This synthesis made an epoxy resin modified by polyetheramines. PART G - Evaluation of 1K adhesives: TEST METHOD:
[0142] All mechanical properties were tested on a 1 mm thick hot dip galvanized (HDG) substrate as supplied by Hovelmann & Lueg GmbH, Germany. The curing conditions for all tests were 177 ° C (350 ° F) for 30 minutes.
[0143] An extension to the ISO11343 method for shim impact, "Adhesives - Determination of dynamic strength for cleavage of the high strength adhesive bond under impact conditions - shim impact method" was used as described in the Test Method Ford BU121-01. Three types of connections were prepared for each condition and test.
[0144] Preparation of the wedge impact connection: coupons cut in 90mm x 20mm. Tape put the TeflonTM tape around the coupons (on both, top and bottom coupons) 30.0 + 2.0 mm on one side. Then applying the adhesive to the top 30 mm. The thickness of the connecting line is maintained with 0.25 mm (10 thousandths) of the glass beads. Remove the adhesive by pressing the edges of the species with a spatula. The specimens stuck together to maintain the vigor of the coupon end and side. The bonding of the arrangements is cured at 350 ° F (177 ° C) for 30 minutes. Then remove any excess adhesive from the edges by sand and ensure an impact on the flat, parallel end allowing a hammer to impact the entire specimen simultaneously. The marks on the coupons 40.0 + 0.2 mm from the attached end as a locator for consistent placement on the shim. Place the species on the wedge, aligning the mark on the specimen with the tip of the wedge, so that it is in the same place on the wedge in each period. No premixing of the specimen, however, allowed the unbound portion of the specimen to conform to the shape of the wedge when the specimen is placed on the wedge. In the Instron Dynatup Model 8200 impact test framework together with an integrated software package, it provided the means for applying the load and the acquisition data respectively. The test structure was assembled with the objective of obtaining a minimum impact energy of 150 Joules (110,635 pounds * feet) and an impact speed of at least 2 meters / second (6.562 feet / second).
[0145] The connections were conditioned at room temperature for at least 24 hours. The connections were pulled using an Instron model 5567 tension mode.
[0146] Lap shear test: 25 mm x 100 mm coupons were cut and delimited on one side by 12.5 mm. The adhesive was applied uniformly to one of the coupons within the defined area for each connection arrangement. The uniformity of the connection thickness was guaranteed by the addition of 0.25 mm (10 thousandth) glass spacer beads. The spacer beads were sprinkled evenly over the material, covering no more than 5% of the total bonding area. The other test coupon was placed over a connection area and spring-loaded clips, such as Office Max binder clips or Home Depot mini-clips, were attached to retain the arrangement together during cooking. The excess adhesive that was compressed was removed with a spatula before cooking. The bonding arrangements were cured as specified, and after cooling, the remaining excess was sanded. The connections were conditioned at room temperature for at least 24 hours. The connections were pulled using an Instron model 5567 tension mode.
[0147] T-shell: cut metallic substrates in pairs of 25 mm x 87.5 mm in dimension. Make a 90 ° bend in 12.5 mm from one end on one side so that the pieces in pairs have a T-shaped configuration: when connected together. Apply a thin layer of the adhesive over three-inch portions on the connection side of a piece. Apply 0.25 mm diameter glass spacer beads evenly over the total bonding area making sure to cover 5% of the total bonding area. Put two pieces together forming a t-shape configuration known as the T-shell arrangement (“T-PEEL”). Place 3 medium binding clips on the T-shell arrangement to hold it together. Remove the excess by compressing the adhesive with a spatula before cooking the arrangement in a pre-conditioned oven at a specified specified temperature. Allow the sample to cool, then remove the connecting clips, and scrape off any remaining excess by compression. Pull the samples with an INSTRON 5567 at a rate of 127 mm per minute. The T-shell arrangements in the INSTRON clamps are conditioned in an ambient camera for at least 30 minutes and tested inside the camera in the case of -30 ° C test. Instron 5567 calculates the results in pounds per linear inch or Newton per mm using the internal computer program. Evaluation of 1K adhesive compositions with various epoxy capped flexibilizers and rubber particles having a core / shell structure:
[0148] The following examples compare 1K adhesive compositions according to certain embodiments of the present invention. The formulations are shown in Table 5 and the mechanical performance of the 1K adhesive compositions is shown in Tables 6-9, respectively.
18. Example of synthesis of Example 2, Part D above. 19. Example of synthesis of Example 2, Part E above. 20. Core / shell poly (butadiene) rubber dispersion (33%), Epon® 828, available from Kaneka Texas, Corporation. 21. Example of synthesis of Example 2, Part A above. 22. Example of synthesis of Example 2, Part F above. 23. Example of synthesis of Example 2, Part B above. 24. Example of synthesis of Example 2, Part C above. 25. Latent heat activated curing agent, available from ALZ Chem. 26. Catalytically active substituted urea, available from ALZ Chem. 27. carbon black, available from Phelps Dodge - Collumbian Chemicals. 28. calcium oxide, available from Mississipi Lime, Co. 29. Hydrophobic fumed silica, available from Wacker Chemie Ag.

[0149] Although particular embodiments of this invention have been described above for illustrative purposes, it should be apparent to the skilled artisan, that many variations of the details of the present invention can be made, without departing from the invention, as defined in the appended claims.

权利要求:
Claims (19)
[0001]
1. Structural adhesive composition, characterized by the fact that it comprises: (a) a first component containing: (1) an epoxy adduct which is the reaction product of reagents comprising a first epoxy compound, a polyol, and an anhydride and / or a diacid; and (2) a second epoxy compound; (b) rubber particles having a core / shell structure; and (c) a second component that reacts chemically with said first component; and (d) graphene carbon particle.
[0002]
2. Composition, characterized by the fact that it comprises: (a) a first component comprising: (1) an epoxy adduct which is the reaction product of reagents comprising a first epoxy compound, a polyol, and an anhydride and / or a diacid ; and (2) a second epoxy compound; (b) graphene carbon particles; and (c) a second component that chemically reacts with said first component.
[0003]
3. Coated substrate, characterized by the fact that it comprises the composition as defined in claim 2.
[0004]
4. Composition, characterized by the fact that it comprises: (a) an epoxy-capped flexibilizer which is the reaction product of reagents comprising an epoxy compound, a polyol, and an anhydride and / or a diacid; and (b) a heat activated latent curing agent; and (c) graphene carbon particles.
[0005]
5. Composition according to claim 4, characterized in that it additionally comprises (d) rubber particles having a core / shell structure.
[0006]
6. Composition according to claim 4, characterized by the fact that it additionally comprises (d) an epoxy / CTBN adduct.
[0007]
7. Composition according to claim 4, characterized in that it additionally comprises (d) an epoxy acid / dimer adduct.
[0008]
8. Composition according to claim 4, characterized by the fact that it additionally comprises (d) an epoxy / CTBN adduct; and (e) an epoxy / dimer acid adduct.
[0009]
9. Composition, characterized by the fact that it comprises: (a) an epoxy capped flexibilizer which is the reaction product of reagents comprising an epoxy compound, an anhydride and / or a diacid; and a caprolactone; (b) a heat activated latent curing agent; and (c) graphene carbon particles.
[0010]
10. Composition according to claim 9, characterized in that it additionally comprises (d) rubber particles having a core / shell structure.
[0011]
11. Composition, according to claim 9, characterized by the fact that it additionally comprises (d) an epoxy / CTBN adduct.
[0012]
12. Composition according to claim 9, characterized in that it additionally comprises (d) an epoxy / dimer acid adduct.
[0013]
13. Composition according to claim 9, characterized by the fact that it also comprises (d) an epoxy / CTBN adduct; and (e) an epoxy / dimer acid adduct.
[0014]
Composition according to claim 9, characterized in that said epoxy capped flexibilizer comprises the reaction product of reagents comprising an epoxy compound, an anhydride and / or a diacid, a caprolactone; and a top functional diamine or amine.
[0015]
15. Composition, characterized by the fact that it comprises: (a) an epoxy-capped flexibilizer that is the reaction product of reagents comprising an epoxy compound and a primary or secondary polyether amine; (b) a heat activated latent curing agent; and (c) graphene carbon particles.
[0016]
16. Composition according to claim 15, characterized in that it additionally comprises (d) rubber particles having a core / shell structure.
[0017]
17. Composition according to claim 15, characterized by the fact that it additionally comprises (d) an epoxy / CTBN adduct.
[0018]
18. Composition according to claim 15, characterized in that it additionally comprises (d) an epoxy / dimer acid adduct.
[0019]
19. Composition, according to claim 15, characterized by the fact that it additionally comprises (d) an epoxy / CTBN adduct; and (e) an epoxy / dimer acid adduct.

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同族专利:

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公开号 | 公开日

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BR112014013594A8|2017-06-13|

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CN104053694A|2014-09-17|

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RU2595040C2|2016-08-20|

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AU2012347650A1|2014-06-26|

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RU2014127905A|2016-02-10|

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KR20140101838A|2014-08-20|

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MX2014006899A|2015-05-15|

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WO2013086277A3|2013-08-15|

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BR112014013594A2|2017-06-13|

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US20120129980A1|2012-05-24|

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CN104053694B|2016-08-17|

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WO2013086277A2|2013-06-13|

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CA2858186C|2016-06-07|

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IN2014DN04651A|2015-04-03|

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EP2788397A2|2014-10-15|

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AU2012347650B2|2015-09-17|

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SG11201403003SA|2014-07-30|

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KR101684752B1|2016-12-08|

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CA2858186A1|2013-06-13|

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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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2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-05| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |

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申请号 | 申请日 | 专利标题

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US13/315,518|2011-12-09|

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