Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22C—FOUNDRY MOULDING
  • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
  • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
  • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
  • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
  • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • B22C1/2273—Polyurethanes; Polyisocyanates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22C—FOUNDRY MOULDING
  • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
  • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
  • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
  • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
  • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • B22C1/2246—Condensation polymers of aldehydes and ketones
  • B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
  • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/54—Polycondensates of aldehydes
  • C08G18/542—Polycondensates of aldehydes with phenols

Definitions

• the present invention relates to foundry binder systems forming a curable polyurethane with a catalytically effective amount of a curing catalyst, comprising at least one phenolic resin component comprising at least: a phenolic resin and a triacetin solvent of the phenolic resin and a polyisocyanate component.
• the invention also relates to foundry mixes prepared from the binder and aggregate, foundry shapes such as cores and molds prepared by the cold or cold box processes, and the respective processes.
• the foundry shapes obtained by the present invention are used in particular to manufacture metal parts, in particular for casting metal parts.
• a conventional method used in the foundry industry to manufacture metal parts is sand casting.
• disposable foundry shapes such as molds and cores, are produced by shaping and curing a foundry binder system which consists of a mixture of sand and binder.
• the binder is used to strengthen mussels and cores.
• the steps that follow the hardening of the binder are as follows:
• the molten metal is poured to fill the hardened mold
• the sand is eventually reused in another binder system.
• Two of the main processes used in sand casting to produce molds and cores are the no-bake process and the cold box process.
• a liquid curing agent is mixed with an aggregate, usually sand, and shaped to produce a cured mold and / or core.
• the no-bake process is based on curing two or more binder components at room temperature after they have been combined with sand.
• the curing of the binder system begins immediately after the addition of a liquid curing agent to all components, producing a cured mold and / or a core.
• a gaseous curing agent is passed through a shaped compacted mixture to produce a cured mold and / or core.
• the term "cold box process” involves the curing at room temperature of a mixture of binder and sand accelerated by a vapor or gas catalyst which has passed through the sand.
• Polyurethane-forming binders cured with a tertiary amine gas catalyst, are often used in the cold box process to hold the foundry aggregates together in a mold or core form as described in US Pat. No. 3,409,579.
• the polyurethane-forming binder system is generally comprised of a phenolic resin component and a polyisocyanate component that are mixed with sand prior to compacting and curing to form a casting binder system.
• a solvent is that which is suitable both for the phenolic resin component and for the polyisocyanate component, and, if necessary, for other additives of the binder, for example, the hardening component. polyisocyanate.
• the oldest class of solvents in this technology are probably those of aromatic hydrocarbon compounds, for example benzene, toluene, xylene and ethylbenzene.
• Certain particular esters are also known as phenolic resin solvents used in polyurethane forming binder systems.
• Some examples are dioctyl adipate and propylene glycol monomethyl ether acetate (WO 8907626), dibasic esters (WO9109908); ethyl acetate (EP1809456); methyl decanoate, methyl undecanoate and vinyl decanoate (RD425045); 1,2-diisobutylphthalate, dibasic esters and butyldiglycol acetate (EP1074568), dialkyl esters (US5,516,8, US 4,852,629).
• esters that is to say the diesters of acetic acid such as glycerol triacetate (or triacetin, RN 102-76-1), glycerol diacetate (or diacetin, RN2539531-7), and glycerol monoacetate (or monoacetin, RN 26446-35-5), alone or in admixture with each other, are also known to be useful in foundry binding systems, but only in as curing agents, for example as described in JP4198531, US5602192, US5169880, US5043412, CS258845, JP03018530, US4468359, US3920460.
• the typical content of triacetin as catalyst in the prior art is 0.5% by weight based on the weight of the phenolic resin.
• the present invention relates to the discovery, undisclosed or suggested in the prior art, that triacetin or mixtures of mono-, di- and triacetin are useful solvents for phenolic resins in polyurethane-forming foundry binder systems, alone. or mixed with other solvents.
• the present invention thus relates to the use of a mixture comprising at least triacetin as a solvent useful for phenolic resins in polyurethane-forming foundry binder systems, alone or in admixture with other solvents.
• the present invention also relates to a curable polyurethane casting binder system with a catalytically effective amount of a curing catalyst comprising at least:
• Another aspect of the present invention relates to foundry mixtures comprising components A and B above with an aggregate, for example sand.
• the present invention relates to a method for preparing a foundry form by the cold box process or the non-baking process, which involves curing the molds and cores prepared with the binder above, or the foundry mix above.
• the catalyst is in particular a tertiary amine.
• the qualities of the triacetin solvent of the phenolic resin according to the present invention are as follows, in comparison with solvents of the prior art:
• N2 nitrogen compounds
• the solvent according to the invention thus comprises at least triacetin.
• This triacetin can be obtained from a process using crude glycerine, such as, for example, the process described in patent application EP2272818.
• the solvent may be a mixture comprising at least triacetin, and monoacetin and / or diacetin.
• the solvent may be a mixture comprising at least 80% by weight of triacetin.
• the mixture comprises triacetin, monoacetin and diacetin.
• the solvent is a mixture of 80 to 95% by weight of triacetin, 5 to 15% by weight of diacetin and less than 5% by weight. monoacetin, based on the total weight of said mixture.
• Triacetin has the formula (AcO) -CH 2 -CH (OAc) -CH 2 (OAc).
• Diacetin has the formula (AcO) -CH 2 -CH (OH) -CH 2 (OAc).
• Monoacetin has the formula (AcO) -CH 2 -CH (OH) -CH 2 (OH).
• triacetin industrial triacetin is a mixture containing from 80 to 95% by weight of triacetin, 5 to 15% by weight of diacetin and less than 5% by weight of monoacetin, relative to the total weight of said mixture. It is advantageously used as a solvent for the phenolic resin in the foundry binder system according to the invention.
• An appropriate mixture of solvents for phenolic resins according to the present invention without excluding any other, concerns triacetin and esters such as are known and generally used in this type of application.
• examples that may be mentioned include dioctyl adipate and propylene glycol monomethyl ether acetate (WO 8907626), dibasic esters (WO9109908); ethyl acetate (EP1809456); methyl decanoate, methyl undecanoate and vinyl decanoate (RD425045); 1,2-diisobutylphthalate, dibasic esters and butyldiglycol acetate (EP1074568), dialkyl esters (US5,516,8, US4,852,629).
• a particular suitable solvent mixture of phenolic resins according to the present invention includes triacetin and a mixture of dimethyl esters, for example that sold in Brazil under the trademark Rhodiasolv RPDE, comprising dimethyl adipate (RN 627-93-0), dimethyl glutarate (RN1119-40-0) and dimethyl succinate (RN 106-65-0), also used as a phenolic resin solvent useful in binding systems foundry forming polyurethane especially in the process without cooking or cold box.
• Rhodiasolv RPDE dimethyl adipate
• RN1119-40-0 dimethyl glutarate
• RN 106-65-0 dimethyl succinate
• adequate proportions of the triacetin solvent and said dimethyl ester mixture vary from 1:20 to 20: 1.
• phenolic resin solvents for example aromatic hydrocarbons such as benzene, toluene, xylene, alkylbenzenes such as ethylbenzene, can also be used with triacetin, or with a mixture of solvents including triacetin and dimethyl esters.
• the phenolic resin component of the present invention is used as a triacetin organic solvent solution, per se or with co-solvents.
• Suitable phenolic resins are those which are known to those skilled in the art, solid or liquid, but soluble in organic solvents.
• the amount of solvent used in component A should be sufficient to result in a binder composition that allows uniform coating thereof on the aggregate and uniform reaction of the mixture.
• concentration of specific solvents varies according to the type of phenolic resin used and its molecular weight, the concentration of solvent in component A in general can be up to 60% by weight of the resin solution, being typically in the range of 10% to 40%, preferably 10 to 30%.
• a particular phenolic resin used in sand casting according to the present invention is a phenolic resole resin, known as benzylic ether resole phenolic resins, prepared by reacting an excess of aldehyde with a phenol in the presence of a phenolic resin. alkaline catalyst or a metal catalyst. Without excluding others, the suitable phenolic resins are preferably substantially free of water. Examples of phenolic resins used in the compositions of the binders in question are well known in the art, such as those described in US Pat. No. 3,485,797. These resins mainly contain bridges connecting the phenolic rings of the polymer, which are ortho-ortho benzyl ether bridges.
• phenols used to prepare resol phenol resins include one or more of the phenols which have hitherto been employed in the formation of phenolic resins and which are unsubstituted or at two positions. ortho either on an ortho position and on the para position. These unsubstituted positions are necessary for the polymerization reaction.
• any of the remaining carbon atoms of the phenolic ring may be substituted.
• the nature of the substituent can vary widely provided that the substituent does not seriously impair the polymerization of the aldehyde with phenol at the ortho and / or para position.
• the substituted phenols used in the formation of phenolic resins include substituted alkyl phenols, substituted aryl phenols, substituted cycloalkyl phenols, substituted aryloxy phenols, and substituted halogenated phenols, which substituents contain from 1 to 26 carbon atoms and preferably from 1 to 12 carbon atoms.
• Suitable phenols include phenol, 2,6-xylenol, o-cresol, p-cresol, 3,5-xylenol, 3,4-xylenol, 2,3,4-trimethyl phenol , 3-ethyl phenol, 3,5-diethyl phenol, p-butyl phenol, 3,5-dibutyl phenol, p-amyl phenol, p-cyclohexyl phenol, p-octyl phenol, 3,5 dicyclohexyl phenol, p-phenyl phenol, p-crotyl phenol, 3,5-dimethoxyphenol, 3,4,5-trimethoxyphenol, p-ethoxyphenol, p-butoxyphenol, 3-methyl -4-methoxy phenol, and p-phenoxy phenol. Phenols of multiple rings such as bisphenol A are also suitable.
• Suitable aldehydes used to react with phenol to obtain a phenolic resole resin have the formula R-CHO where R is a hydrogen atom or a hydrocarbon radical with 1 to 8 carbon atoms.
• the phenol-reactive aldehydes may include one of the aldehydes used hitherto in the formation of phenolic resins such as formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde, and benzaldehyde.
• the polyisocyanate component of the binder of the present invention comprises a polyisocyanate, a polyisocyanate solvent and optional ingredients.
• the polyisocyanate has a functionality of two or more, preferably from 2 to 5. It may be aliphatic, cycloaliphatic, aromatic, or a hybrid polyisocyanate.
• the polyisocyanates may also be protected polyisocyanates, polyisocyanate prepolymers and quasi-prepolymers of polyisocyanates. Polyisocyanate blends are also covered by the present invention.
• the polyisocyanate component of the foundry binder comprises a polyisocyanate, generally an organic polyisocyanate, and an organic solvent, generally comprising aromatic hydrocarbons, such as benzene, toluene, xylene and / or alkylbenzenes, in amounts typically ranging from from 0 percent by weight to about 80 percent by weight, based on the weight of the polyisocyanate.
• aromatic hydrocarbons such as benzene, toluene, xylene and / or alkylbenzenes
• Optional ingredients such as release agents and life extenders may also be used in the polyisocyanate component.
• polyisocyanates used in the present invention are aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, and aromatic polyisocyanates such as 2,4 and 2 , 6-toluene diisocyanate, diphenylmethane diisocyanate, and their dimethyl derivatives.
• polyisocyanates are 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene, and their methyl derivatives, polymethylenepolyphenyl isocyanates, chlorophenylene-2,4-diisocyanate, and the like.
• the polyisocyanates are used in concentrations sufficient to cause curing of the resin after gas passage or when in contact with the liquid curing catalyst.
• the ratio of the polyisocyanate to the hydroxyl of the phenolic resin is 1.25: 1 to 1: 1, 25.
• the amount of polyisocyanate used is generally from 10 to 500 percent by weight, based on the weight of the phenolic resin.
• Suitable polyisocyanates are used in particular in liquid form, which can be used in undiluted form, while solid or viscous polyisocyanates are used in the form of organic solvent solutions.
• suitable solvents for polyisocyanate are AB9 and AB10 (alkylbenzene compounds containing an alkyl substituent which comprises respectively 9 and 10 carbon atoms, for example sold under the trade name Solvesso 100).
• aromatic solvents of the polyisocyanates include benzene, toluene, xylene, alkyl benzenes and mixtures thereof.
• the aromatic solvents are preferably a mixture of aromatic solvents whose boiling point ranges from 125 ° C to 250 ° C.
• the polar solvents must not be extremely polar, which would make them incompatible with the aromatic solvent.
• Suitable polar solvents are generally those which are classified in the art as coupling solvents and include furfural, furfuryl alcohol, 2-ethoxyethyl acetate (Cellosolve TM acetate), 2-butoxyethanol (butyl Cellosolve TM), monobutyl ether diethylene glycol (butyl Carbitol TM), diacetone alcohol, and 2,2,4-trimethyl-1,3-diol monoisobutyrate (Texanol TM). Cellosolve, Carbitol, and Texanol are trade names.
• the polyisocyanate component B optionally comprises an aromatic hydrocarbon compound.
• An optional element for a polyurethane forming binder system is a natural oil.
• the natural oil is used in the phenolic resin component, the isocyanate component, or both, in an effective amount sufficient to improve the tensile strength of the binder-based foundry forms. This amount is generally from about 1 percent by weight to about 15 percent by weight, based on the weight of the isocyanate component. In general, lesser amounts of natural oil are used in the phenolic resin component, generally from about 1 percent by weight to about 5 percent by weight, based on the weight of the phenolic resin. Compatible natural oils are also adequate.
• a natural oil is considered compatible with organic isocyanate and / or phenolic resin if the mixture does not separate in two phases at room temperature, and preferably if it does not separate at temperatures between 30 ° C at 0 ° C.
• Natural oils include unmodified natural oils and their various known modifications, for example heat-thickened oils blown with air or oxygen, such as flaxseed oil and oil. Soy soufflé. They are generally classified as esters of ethylenically unsaturated fatty acids. The proper viscosities of the natural oil range from A to J according to the Gardner Holt viscosity index.
• the acidity value of the natural oil varies typically from 0 to 10, as measured by the number of milligrams of potassium hydroxide required to neutralize a sample of 1 gram of natural oil.
• Representative examples of the natural oils that are used in the isocyanate component include linseed oil, including refined linseed oil, epoxidized linseed oil, linseed oil refined with alkali, soybean oil, cottonseed oil, RBD (refined, bleached and deodorized) canola oil, refined sunflower oil, tung oil and dehydrated castor oil.
• Particularly used natural oils include more pure forms of natural oils which are treated to remove fatty acids and other impurities, generally consisting of triglycerides and less than 1 percent by weight of impurities such as fatty acids and other impurities.
• Particular examples of such pure natural oils include Polymerized Linseed Oils (PLO) such as Supreme Linseed Oil with an acid value of about 0.30 and a maximum viscosity of A and soybean oils.
• Purified oils such as refined soybean oil having an acid value of less than 0.1 and a viscosity of A to B. As is already known, this increases the tensile forces of foundry shapes.
• drying oils as described in US Pat. No. 4,268,425 can be included in the binder in one of the solvents mentioned herein. These drying oils comprise fatty acid glycerides containing two or more double bonds. In addition, ethylenically unsaturated fatty acid esters such as pine oil esters of polyhydric or monohydric alcohols can be used as the drying oil. Generally, the drying oils are used at about 35% to about 50% by weight of the total amount of solvent.
• the binder may also contain a silane, generally added to the phenolic resin component, for example as described in US6288139. For example, the silane is added to the phenolic resin component in amounts of 0.01 to 2 percent by weight, based on the weight of the phenolic resin.
• ordinary sand-type foundry shapes refers to foundry shapes that have sufficient porosity to permit evacuation of volatiles during the casting operation.
• at least about 80% by weight of the aggregates used for foundry shapes have an average particle size of not less than about 50 and about 50 mesh (Tyler Screen Mesh).
• a suitable aggregate used for ordinary foundry shapes is silica in which about 70% by weight of the sand is silica.
• Other suitable materials include zircon, olivine, aluminosilicate, sand, chromite sand, and the like. Although the best results are often obtained when the aggregate used is dry, it may contain small amounts of moisture.
• the aggregate constitutes the main constituent, the binder being present in a relatively small amount.
• the amount of binder does not generally exceed about 10% by weight and is frequently in the range of 0.5 to 7% by weight based on the weight of the aggregate, particularly 0 to 1, 8%.
• the binder compositions are preferably provided as a double package system with the phenolic resin component in one package and the polyisocyanate component in the other.
• the phenolic resin component is mixed with the aggregate, and then the polyisocyanate component is added. Binder distribution methods on aggregate particles are well known to those skilled in the art.
• Another aspect of the present invention relates to methods for obtaining sand casting forms, using the novel binder system, which is molded into the desired shape, such as a mold or core, and cured.
• Curing by the cold box process is carried out by passing a tertiary volatile amine, for example triethylamine, 1-dimethylamino-2-propanol (DMA-2P), monoethanolamine or dimethylaminopropylamine (DMAPA), through the form in the mold as described in US Patent 3,409,579.
• Curing by the non-firing process is performed by mixing a liquid amine curing catalyst in the foundry binder system, which is then shaped, and set to cure.
• the term "catalytically effective amount of a curing catalyst” a concentration of the catalyst preferably between 0.2 and 5.0 percent by weight of the phenolic resin.
• the useful liquid curing catalyst amines have a pKb value generally of the order of 7 to 11. Particular examples of these amines include 4-alkylpyridines, isoquinoline, arylpyridines, 1-methylbenzimidazole, and 1,4-thiazine.
• a tertiary liquid amine particularly used as catalyst is an aliphatic tertiary amine such as tris (3-dimethylamino) propylamine).
• the concentration of the liquid amine catalyst ranges from 0.2 to 5.0 percent by weight of the phenolic resin, in particular from 1.0 to 4.0 percent by weight, more preferably 2.0. to 3.5 percent by weight based on the weight of the polyether polyol.
• Catalysts such as triethylamine or dimethylethylamine are used in a range of 0.05 to 0.15 percent by weight based on the weight of the binder.
• the solubilization power of the solvents tested in this example was determined by simulation using Solsys ® software (Rhodia). It is based on Hansen's solubility parameter theory and three-dimensional system. As it is in fact known to those skilled in the art, the most widely used cohesion energy parameters for the characterization of solvents are those developed by Hansen (for example in the work "Hansen Solubility Parameters: A user's handbook”. Hansen, Charles Second Edition 2007 Boca Raton, FL, USA (CRC Press). There are three numbers that together are called HSPs. They fully describe how a solvent behaves relative to what is dissolved if their HSPs are known or can be estimated:
• the technique for determining the solubility parameters D, P, H of a substance consists in testing the solubility of said substance in a series of pure solvents which belong to different chemical groups (for example, hydrocarbons, ketones, esters, alcohols and glycols). The evaluation is made by considering the solvents which completely solubilize, partially or do not solubilize the substance to be solubilized.
• the Solsys® Software is used to determine the solubility volume of the substance and as a result it determines the best solvent for dissolving the substance.
• the volume of solubility is represented by a sphere (three-dimensional system) whose center corresponds to a "standardized distance" equal to 0 and represents the maximum of solubility.
• the set of points on the surface of the sphere correspond to a "standardized distance” equal to 1 and reflect the limit of solubility.
• the sphere is represented on a graph whose axes correspond to ⁇ D, ⁇ and ⁇ .
• the solubility of the resin in the solvent will be all the better that the volume of solubility will be close to the center (normalized distance equal to 0). Beyond the surface of the sphere (normalized distance equal to 1), the resin is no longer soluble in the solvent.
• Standardized distance values are used to evaluate the solubilizing power of a substance, i.e. phenolic resin in this case, in a solvent. The more the value of the normalized distance is close to zero, the more the resin is soluble in the solvent. Table I below shows the solubility parameter values of a commercial mixture of dimethyl esters, compared with triacetin with purity higher than 99.5% and industrial triacetin. Standardized distances were obtained for a phenolic resole resin. TABLE I
• solubility parameter values for the commercial dimethyl ester solvent mixture are similar to those obtained for triacetin. This means that the solvents are partially or totally interchangeable for most applications, especially in blending, which depends on commercial conditions. Standard distances are also very close, especially for solubility in RPDE and triacetin with purity higher than 99.5%.

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• 2011
  • 2011-03-22 FR FR1152347A patent/FR2972946B1/fr not_active Expired - Fee Related
• 2012
  • 2012-03-20 BR BR112013023910A patent/BR112013023910A2/pt not_active IP Right Cessation
  • 2012-03-20 EP EP12718327.5A patent/EP2688698A1/fr not_active Withdrawn
  • 2012-03-20 CN CN2012800142919A patent/CN103442824A/zh active Pending
  • 2012-03-20 US US14/001,241 patent/US20140018468A1/en not_active Abandoned
  • 2012-03-20 WO PCT/IB2012/000539 patent/WO2012127299A1/fr active Application Filing
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