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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22C—FOUNDRY MOULDING
  • B22C5/00—Machines or devices specially designed for dressing or handling the mould material so far as specially adapted for that purpose
  • B22C5/08—Machines or devices specially designed for dressing or handling the mould material so far as specially adapted for that purpose by sprinkling, cooling, or drying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
  • B22D29/00—Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
  • B22D29/00—Removing castings from moulds, not restricted to casting processes covered by a single main group; Removing cores; Handling ingots
  • B22D29/001—Removing cores
  • B22D29/002—Removing cores by leaching, washing or dissolving
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
  • B22D31/00—Cutting-off surplus material, e.g. gates; Cleaning and working on castings
  • B22D31/002—Cleaning, working on castings

Definitions

• the present invention relates to a method of disintegrating a foundry mold comprising sand and a polyurethane binder.
• the present invention further relates to a method of disintegrating a foundry mold by contacting it with a composition comprising at least one carboxylic acid amide and at least one alkanolamine.
• sand casting All foundries produce castings by pouring molten metal into molds.
• the most common type of casting process is known as sand casting.
• Sand is used in two different ways in metal casting: as a molding material, which forms the external shape of the cast part, and as cores, which form internal void spaces in products such as engine blocks. Since sand grains do not naturally adhere to each other, binders must be introduced to cause the sand to stick together and hold its shape during the introduction of the molten metal into the mold and the cooling of the casting.
• Sand casting involves manufacturing a pattern of the component to be cast, and packing sand around the pattern to produce a hollow mold. Molds are typically made in two halves to facil itate removal of the pattern, and then the molds are assembled to form a "hollow" that matches the pattern's shape. Cores made of packed sand with special binders may be in serted into a mold, prior to assembly, to form interior surfaces for complex shapes. Molten metal is poured into the mold cavity and allowed to solidify and cool. The casting is shaken out of the sand mold using vibratory machines, mechanically cleaned of extraneous metal by cutting or grinding, and blast cleaned to remove casting sand and other surface contaminants.
• the foundry industry generates a number of by-products, of which the largest volume is a “spent sand” that consists of sand with residuals of binders.
• sand casting generates residuals from metal melting and pouring, and molding processes. It is standard foundry practice to reuse molding and core making sands. Residual sand is routinely screened and returned to the system for reuse.
• sand molds which entail both me chanical and chemical actions.
• abrasive cleaning methods such as sand blasting.
• Chemical methods of cleaning which are available to the industry, however, produce cleaner castings than the foregoing mechanical procedures. This is ef fected because a great deal of trouble is occasioned by the retention of the granular sand on the casting by reason of the adhesive properties of the decomposition products of the organic binders.
• the adhering sand particles are immune to removal by abrasive cleaning methods and they can only be removed by attacking and dissolving the residual si liceous particles with a chemical reagent.
• sand molds can be disintegrated by treating them with the compositions or chem icals which dissolve the synthetic binders, and the sand can then be processed and reused.
• US 2,666,001 discloses the removal of residual sand from the cast by immersing in a liquid bath comprising a strongly acidic solution of fluorophosphoric acid followed by neutralization. Fluorophosphoric acid being highly toxic and corrosive, it is difficult to implement the process on a large scale.
• US 2,766,496 discloses a process of cleaning used foundry sand which comprises the steps of screening the sand in presence of water to remove oversized adventitious material, fluid izing the sand with a jet of water and passing it to relatively quiescent settling zones wherein loose carbonaceous impurities are floated off.
• the disadvantage of the process is that huge volumes of water waste are generated.
• the presently claimed invention is directed to a method for disintegrating a foundry mold comprising sand and a polyurethane binder comprising the step of
• R x denotes linear or branched, unsubstituted or hydroxy substituted C 2 -C 22 alkyl
• R 2 and R 3 independently of each other, denote FI or linear or branched, unsubstituted or substituted C -C alkyl;
• AO is, identical or different, selected from the group consisting of CH 2 -CH 2 -0, CH (CH 3 )- CH 2 -0, CH 2 -CH (CH 3 )-0, CH (C 2 H 5 )-CH-0, C(CH 3 ) 2 -CH 2 -0, CHC(CH 3 ) 2 -0 and CH 2 - CH (C 2 H 5 )-, m is 1, 2, 3, 4, 5, 6 or 7, and x, y independently of one another are 0 or 1
• the presently claimed invention is directed to a composition
• a composition comprising
• composition comprising (a) at least one carboxylic acid amide of general formula (I)
• Ri denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl
• the presently claimed invention is directed to the use of the composi tion comprising
• the presently claimed invention is directed to a method for disinte grating the foundry mold comprising sand and a polyurethane binder
• a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only.
• the terms “first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)” etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embod iments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
• first”, “second”, “third” or“(A)”,“(B)” and“ (C)” or “(a)”, “(b)”, “(c)”, “(d)”, “i”, “ii” etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, that is, the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below.
• R x denotes linear or branched, unsubstituted or hydroxy substituted C 2 -C 22 alkyl
• R 2 and R 3 independently of each other, denote H or linear or branched, unsubstituted or substituted C C 12 alkyl;
• AO is, identical or different, selected from the group consisting of CH 2 -CH 2 -0, CH (CH 3 )-CH 2 -0, CH 2 -CH (CH 3 )-0, CH (C 2 H 5 )-CH-0, C(CH 3 ) 2 -CH 2 -0, CHC(CH 3 ) 2 -0 and CH 2 -CH (C 2 H 5 )-0
• n 1, 2, 3, 4, 5, 6 or 7, and
• x, y independently of one another are 0 or 1
• the term ‘disintegrating’ includes cleaning of foundry molds of residual sand and binder which are left on it after the molding process. Additionally, it also covers the‘complete breaking of the foundry mold’ wherein the sand and binder is separated and the sand can be recycled. Accordingly, a mixture of sand and binder refers to a mixture in which the sand and the binder are present in form of discrete materials.
• ‘Foundry mold’ herein refers to molds made of sand and binder.
• Contacting denotes immersing the foundry mold in the composition. It may also include adding the composition on to a metal cast. When the foundry mold is immersed in the composition, it disintegrates into sand and binder. In case when the composition is added on to a metal cast, it is done to clean the metal cast of the residual sand and binder mixture, after the process of casting.
• C 1 -C 12 -alkyl covers acyclic saturated hydrocarbon residues, which may be linear or branched and unsubstituted or at least mono-substituted with, as in the case of C 1 -C 12 -alkyl, 1 to 12 (i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12) carbon atoms.
• C 2 -C 22 -alkyl covers acyclic saturated hydro carbon residues, which may be linear or branched and unsubstituted or at least mono-sub- stituted with, as in the case of C 2 -C 32 -a I ky 1 , 2 to 22 (i.e. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22) carbon atoms.
• Particularly preferred sub stituents may be selected mutually independently from the group consisting of F, Cl, Br, I, - N0 2 , -CN, -OH, -SH, -N H 2 , -N (CH 3 ) 2 , -N (C 2 H 5 ) 2 and -N (CH 3 )(C 2 H 5 ).
• “branched” denotes a chain of atoms with one or more side chains attached to it. Branching occurs by the replacement of a substituent, e.g., a hydrogen atom, with a covalently bonded alkyl radi cal.
• the carboxylic acid amide of general formula (I) has the following structure
• R x denotes linear or branched, unsubstituted or hydroxy substituted C 2 -C 22 alkyl
• R 2 and R 3 independently of each other, denote H or linear or branched, unsubstituted or substituted C C 12 alkyl.
• R x is selected from the group consisting of ethyl, /7-propyl, /7-butyl, /7-pentyl, n- hexyl, /7-heptyl, /7-octyl, /7-nonyl, /7-decyl, /7-undecyl, /7-dodecyl, /7-tridecyl, /7-tetradecyl, n- pentadecyl, /7-hexadecyl, /7-heptadecyl, /7-octadecyl, /7-nonadecyl, /7-eicosyl, /7-heneicosyl, n- docosyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl
• Ri is selected from the group consisting of ethyl, /7-propyl, /7-butyl, /7-pentyl, /7-hexyl, /7-heptyl, /7-octyl, /7-nonyl, /7-decyl, isooctyl, isononyl, isodecyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isodecyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1- hydroxybutyl, 2-hydroxybutyl, 2-hydroxybutyl, 1-hydroxypentyl, 2-hydroxypentyl, 3-hydroxy- pentyl, 4-hydroxypentyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 3-hydroxyhexyl, 4-hydroxyhexyl and 5-hydroxyhexyl.
• Ri is selected from the group consisting of /7-octyl, /7-nonyl, /7-decyl, isooctyl, isononyl, isodecyl and 1-hydroxyethyl. Particularly preferably, Ri is 1-hy- droxyethyl.
• R 2 and R 3 independently of each other, are selected from the group con sisting of H, methyl, ethyl, /7-propyl, /7-butyl, /7-pentyl, /7-hexyl, /7-heptyl, /7-octyl, /7-nonyl, n- decyl, /7-undecyl, /7-dodecyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl and /-butyl.
• R 2 and R 3 independently of each other, are selected from the group consisting of H , methyl, ethyl, /7-propyl, /7-butyl, isopropyl, isobutyl and /-butyl.
• R 2 and R 3 independently of each other, are selected from the group consist ing of methyl, ethyl and /7-propyl.
• R 2 and R 3 are methyl.
• the compound of general formula (I) is 2-hydroxypropana- mide.
• Suitable carboxylic acid amides are known and commercially available under the tradenames Agnique AMD 3L, Agnique ® AM D10 and Agnique AM D 810 from BASF SE.
• the presently claimed invention relates to a method for disinte grating the foundry mold comprising sand and a polyurethane binder comprising the step of (i) contacting the foundry mold with a composition comprising
• AO is, identical or different, selected from the group consisting of CH 2 -CH 2 -0, CH (CH 3 )- CH 2 -0, CH 2 -CH (CH 3 )-0, CH (C 2 H 5 )-CH-0, C(CH 3 ) 2 -CH 2 -0, CHC(CH 3 ) 2 -0 and CH 2 - CH (C 2 H 5 )-0, m is 1, 2, 3, 4, 5, 6 or 7, and x, y independently of one another are 0 or 1; to obtain a mixture of the sand and the polyurethane binder.
• the alkanolamine of general formula (II) has the following structure
• AO is, identical or different, selected from the group consisting of CH 2 -CH 2 -0, CH (CH 3 )- CH 2 -0, CH 2 -CH (CH 3 )-0, CH (C 2 H 5 )-CH-0, C(CH 3 ) 2 -CH 2 -0, CHC(CH 3 ) 2 -0 and CH 2 - CH (C 2 H 5 )-0; m is 1, 2, 3, 4, 5, 6 or 7, and x, y independently of one another are 0 or 1.
• n 1, 2 or 3, more preferably m is 2.
• x and y are both 0. Accordingly, in an embodiment the compound of general formula (I I) is monoethanolamine.
• the presently claimed invention relates to a method for disinte grating the foundry mold comprising sand and a polyurethane binder comprising the step of (i) contacting the foundry mold with a composition comprising
• R x denotes linear or branched, unsubstituted or hydroxy substituted C 2 -C 22 a ⁇ - kyl
• R 2 and R 3 independently of each other, denote H or linear or branched, unsubstituted or substituted alkyl
• the sand is selected from the group consisting of natural silica sand, clay, green sand, quartz sand, chromite sand, olivine sand, special sands and zirconium sand.
• Silica sand in form of granular quarts is the main constituent of molding sand having enough refractoriness which can impart strength, stability and permeability to molding and core sand. But along with silica small amounts of iron oxide, alumina, lime stone (CaC0 3 ), magnesia, soda and potash are present as impurities.
• the chemical composition of silica sand gives an idea of the impurities like lime, magnesia, alkalis etc. present.
• the presence of excessive amounts of iron oxide, alkali oxides and lime can lower the fusion point to a considerable extent which is undesirable.
• the silica sand can be specified according to the sand grain size and the shape (angular, sub-angular and rounded) of the sand.
• Clay sand is the mixture of natural silica sand, clay, additives and water.
• the clay used to make wet clay sand is bentonite clay.
• the compressive strength is generally 0.05 to 0.1 MPa.
• the water content is 3.5 to 5%.
• Green Sand is a mixture of silica sand, chromite sand, or zircon sand, bentonite (clay), inert sludge, anthracite, sometimes with a proportion of olivine, staurolite or graphite.
• Quartz sand contains mainly crystalline silica S i0 2 and additional mineral contents such as feldspars, clay minerals, mica minerals as well as carbonate and carbonaceous components.
• the suitability of quartz grains as molding material is mainly determined by the Si0 2 content. The higher the content, i.e. the fewer additions of low-melting compounds, the more favorable the sand will behave towards high thermal loads.
• Chromite sand is a naturally occurring spinel consisting primarily of the oxides of chrome and iron.
• Olivine sand is composed mainly of silica, magnesium oxide, iron oxide and aluminium oxide. It has a low thermal expansion rate compared to silica sand.
• Special sands include natural mineral sands, sintering and melting products produced in granular form or turned into granular form by breaking, grinding and grading processes, or inorganic mineral sands produced by other physical-chemical methods. Special sands are different from quartz sand, particularly due to their significantly lower thermal expansion be havior within the temperature range of 20 to 600° C, their heat conductivity, refractoriness, and other physical characteristics.
• the sand is silica sand or special sand.
• the polyurethane based binders are polyurethane based binders which may also include, in addition to polyurethane, components such as water glass (sodium silicate) and resins like phenol formaldehyde, urea formaldehyde and furan resins.
• components such as water glass (sodium silicate) and resins like phenol formaldehyde, urea formaldehyde and furan resins.
• Polyurethanes are formed from polyhydroxy compounds and polyisocyanates.
• the polyhy droxy compounds in turn are commonly prepared from phenols and formaldehyde.
• the poly hydroxy component may be any organic hydroxy compound having a functionality of two or more that is soluble in the solvents employed.
• Such polyhydroxy compounds can include sim ple aliphatic polyols, amine polyols, polyether polyols, phenolic resins and mixtures of these.
• the amine polyols are normally produced as the reaction product of an alkylene oxide and an amine compound. In general, any polyol containing at least one or more tertiary amine groups is considered to be within the scope of the definition of "amine polyol".
• the amine compounds which react with alkylene oxides to yield the amine polyols include ammonia and mono- and polyamine compounds with primary or secondary amino nitrogen. Specific examples include aliphatic amines such as primary alkyl amines, ethylene diamine, diethylene triamine and tri ethylene tetraamine, cycloaliphatic amines, aromatic amines, such as ortho-, meta-, and para-phenylene diamines and aniline formaldehyde resins.
• the phenols employed in the formation of such phenolic resins are generally any of the phe nols which may be utilized in the formation of phenolic resins.
• Specific suitable phenols which may be used include phenol, o-cresol, m-cresol, p-cresol, 2, 5-xylenol, 3, 4-xylenol, 3, 5-xy- lenol, 3, 4, 5-trimethylphenol, 2-ethylphenol, 3-ethylphenol, 3, 5-diethylphenol, o-sec-bu- tylphenol, p-butylphenol, 3, 5-dibutylphenol, p-amylphenol, p-cyclohexylphenol, o-octylphe- nol, o-sec-decylphenol, nonylphenol, 3, 5-dicyclohexylphenol, p-phenylphenol, p-crotylphe- nol, 2-methoxyphenol, 3, 5-dimethoxyphenol
• the furan resins that are used for foundry binders are usually prepared from reacting furfuryl alcohol with urea-formaldehyde resins, or with formaldehyde, in order to obtain low-viscosity, soluble, fusible, furan resins. In some cases, phenolic resins or other modifiers are added to the furan resins.
• the aldehyde employed in the formation of the phenolic and furan resin component include any of the aldehydes heretofore employed in the formation of phenolic resins such as formal dehyde, acetaldehyde, propionaldehyde, furfuraldehyde and benzaldehyde.
• the isocyanate component which can be employed in a binder may have a functionality of 2 or more.
• exemplary isocyanates are organic polyisocyanates such as tolylene-2, 4-diisocya nate, tolylene-2, 6-diisocyanate and mixtures thereof, and particularly the crude mixtures thereof that are commercially available.
• polyisocyanates include methylene-bis- (4-phenylisocyanate), n-hexyl diisocyanate, naphthalene-1, 5-diisocyanate, cyclopentylene- 1, 3-diisocyanate, p-phenylene diisocyanate, tolylene-2, 4, 6-triisocyanate and triphenylme- thane-4, 4', 4"-triisocyanate.
• Higher isocyanates are provided by the liquid reaction products of (1) diisocyanates and (2) polyols or polyamines and the like.
• isothiocyanates and mixtures of isocyanates can be employed.
• the many impure or crude polyisocyanates that are commercially available.
• the isocyanate component may addi tionally contain a chlorosilane compound selected from the group consisting of trime- thylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, tetrachlorosilane, diethy- chlorosilane, viny Itrichlorosilane and diphenyldichlorosilane.
• a chlorosilane compound selected from the group consisting of trime- thylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, tetrachlorosilane, diethy- chlorosilane, viny Itrichlorosilane and diphenyldichlorosilane.
• additives include, but are not limited to, amino silanes, epoxy silanes, mercapto silanes, hy droxy silanes and ureido silanes such as, for example, gamma-aminopropyltrimethoxysilane, gamma-hydroxypropyltrimethoxysilane, 3-ureidopropyl triethoxysilane, gamma-mercapto- propyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta-(3, 4-epoxycyclo- hexyOtrimethoxysilane and N-beta-(aminoethyl gamma-aminopropyltrimethoxy silane.
• the composition that is used according to the presently claimed invention further comprises at least one surfactant.
• the at least one surfactant is selected from the group consisting of anionic surfactant, cationic surfactant, non-ionic surfactant and ampho teric surfactant.
• Suitable anionic surfactants are selected from the group consisting of salt of alkyl sulfate, alkyl ether sulfate, a-olefin sulfonate and linear alkyl benzene sulfonate.
• alkyl sulfates are compounds of the formula:
• R denotes linear or branched, unsubstituted C 6 - C 22 alkyl
• M denotes alkali metal or ammonium cation
• C 6 -C 22 -alkyl covers acyclic saturated hydrocarbon residues, which may be linear or branched and unsubstituted having 6 to 22 carbon atoms.
• the alkyl sulfates are obtained by sulfating the higher alcohols ( C 6 - C 22 carbon atoms) proberichtd from the glycerides of tallow, coconut oil, suitable vegetable oil or synthetic alcohols followed by neutralization with alkali hydroxide.
• the alkyl sulfates also contain reaction by-products such as free salt (for example sodium chloride is the free salt by product, when neutralization agent is sodium hydroxide), free fatty alcohol, salt of fatty alcohol. Therefore, the solid content of the alkyl sulfate will be different from the active content.
• Active content denotes‘the amount of alkyl sulfate’ present in the composition whereas the solid content denotes‘a total of alkyl sulfate, fatty alcohol, salt of fatty alcohol and the free salt’ in the composition.
• Free herein denotes that the salt is not bound to the fatty alcohol/ alkyl sulfate by any kind of chemical bonding.
• Alkyl ether sulfates are compounds of the formula
• R’ denotes linear or branched, unsubstituted C 6 - C 22 alkyl
• n is from 1 to 20
• M denotes alkali metal or ammonium cation
• alkyl ether sulfates are produced by the ethoxylation of fatty alcohol and thus will gen erally be obtained in the form of mixtures comprising varying alkyl chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-eth- oxylated alkyl sulfates.
• a-olefin sulfonates are generally produced by sulfonating a -olefin.
• the a -olefins, which are sulfonated to form the surfactants used in the compositions of the present invention may contain from about 10 to 22 carbon atoms and preferably 12 to 18 carbon atoms.
• alpha-olefins are 1-de- cene, 1-undecene, 1-dodccene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene and the like and mixtures of the aforesaid. Sulfonation of these long chain olefins is typically carried out utilizing sulfur trioxide mixed with a diluent.
• a- olefin sulfonates as used herein includes not only the alkene sulfonate itself but also admixtures of same formed as a result of the usual sulfonation neutralization, and hydrolysis procedure with substantial proportions of the corresponding water soluble hydroxyalkane sulfonates.
• Linear alkyl benzene sulfonate (LABS) is produced by sulfonation of linear alkylbenzene (LAB) and subsequent neutralization of the corresponding sulfonic acid (H LAS).
• Linear al kylbenzene is synthesized by the alkylation of benzene with linear olefins.
• Traditional pro Waits for alkylation of aromatics compounds use Friedel-Craft type catalysts, for example, hydrofluoric acid, aluminum trichloride and the like.
• Anionic surfactant may also include alkylamide sulphates of formula
• R 4 denotes a C 2 -C 22 alkyl
• M is a hydrogen atom or an alkali metal cation cation or ethoxylenated (EO) and/or propoxylenated (PO) derivatives thereof, containing on average from 0.5 to 60 EO and/or PO units;
• anionic surfactants are, salts of C 8 -C 24 , saturated or unsaturated fatty acids, alkyl- glyceryl sulphonates, paraffin sulphonates, N-acyl N-alkyltaurates, alkylphosphates, isethio- nates, alkylsuccinamates, alkylsulphosuccinates, sulphosuccinate monoesters or diesters, El- acyl sarcosinates, alkylglycoside sulphates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium or lithium), a substituted or unsubstituted ammonium residue (me thyl-, dimethyl-, trimethyl- or tetramethylammonium, dimethylpiperidinium, etc.) or an alka- nolamine derivative (monoethanolamine, diethanolamine, triethanolamine, etc.) and alkyl or alkylaryl
• Cationic surfactants are a well-known group of surface-active compounds which have at least one active cationic (positive ion) constituent.
• cationic surfactant quaternary ammo nium hydroxides such as octyltrimethylammonium hydroxide, dodecyltrimethylammonium hy droxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide decyldimethylbenzylammonium hydroxide, didodecyldimethylammonium hydroxide, diocta- decyldimethylammonium hydroxide, beef tallow trimethylammonium hydroxide, and coconut oil trimethylammonium hydroxide, and their salts can be exemplified.
• amphoteric surfactants comprise betaines, sulphobetaines and carboxylates and sulphonates of fatty acids and of imidazole, such as alkyldimethylbetaines, alkylamidopropyl- dimethylbetaines, alkyldimethylsulphobetaines or alkylamidopropyldimethylsulphobetaines, such as Mirataine CBS sold by the company Rhodia, and the products of condensation of fatty acids and of protein hydrolysates; alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms; amphoteric alkylpolyamine derivatives such as Amphionic XL ® sold by Rhodia and Ampholac 7T/X ® and Ampholac 7C/X ® sold by Berol Nobel.
• the at least one surfactant is preferably a non-ionic surfactant.
• the at least one non-ionic surfactant is selected from the group consisting of poly(C 2 -C 4 )al- kylene glycol mono-(C 8 -C 22 )-alkyl ether, poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-carboxylic acid ester, alkoxylated oil and alkoxylated alkylamine.
• the poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-alkyl ether is preferably poly(C 2 -C 3 )alkylene glycol mono-(C 8 -C 22 )-alkyl ether.
• Preferred poly(C 2 -C 3 )alkylene glycol mono-(C 8 -C 22 )-alkyl ether are preferably compounds of the formula
• Re is linear or branched C 8 -C 22 -alkyl
• q is a natural number from 1 to 50.
• r is 0 or is a natural number from 1 to 30, with the proviso that 2 ⁇ q + r ⁇ 50.
• poly(C 2 -C 3 )alkylene glycol mono-(C 8 -C 22 )-alkyl ether are preferably compounds of the formula
• R 6 is linear or branched C 8 -C 22 -alkyl
• q is a natural number from 1 to 15;
• r is 0 or is a natural number from 1 to 20, with the proviso that 2 ⁇ q + r ⁇ 30.
• alkyl refers to acynch saturated aliphatic residues, including linear or branched alkyl residues. Furthermore, the alkyl residue is unsubstituted and includes as in the case of C 8 -C 22 alkyl 8 to 22 carbon atoms.
• linear and branched C 8 -C 22 alkyl include, but are not limited to, /7-octyl, /7-nonyl, /7-decyl, /7-undecyl, /7-dodecyl, /7-tridecyl, /7-tetradecyl, /7-pentadecyl, n- hex- adecyl, /7-heptadecyl, /7-octadecyl, /7-nonadecyl, /7-eicosyl, /7-heneicosyl, /?-docosyl, 2- ethylhexyl, 2-propyl-heptyl, 2-butyl-l-octyl, 2-pentyl-l-nonyl, isooctyl, isodecyl, isoundecyl, isododecyl, isotri
• the poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-alkyl ether have a molecular weight of from 300 g/mol to 2000 g/mol determined by X H-N MR spectroscopy using for instance a 400 MHz spectrometer by Bruker.
• the molecular weight can be determined by the integration of the signals of the poly(C 2 -C 4 )alkylene glycol backbone and the comparison of this integral with the integral of the mono-(C 8 -C 22 )-alkyl signals.
• the poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-alkyl ether can be prepared by alkoxylation of fatty alcohol.
• the fatty alcohol R ⁇ OH which is used for the synthesis of poly(C 2 -C 4 )al- kylene glycol mono-(C 8 -C 22 )-alkyl ether is derived from a natural source it is common to have mixtures, e.g. of C 16 and C 18 alcohols or C 12 and C 14 alcohols.
• Fatty alcohol R ⁇ OH can also be synthesized (for example by oxo process) from olefin mixtures and in this case, it is common to have mixtures e.g. of Ci 3 and Ci 5 alcohols.
• Suitable poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-alkyl ether are known and commercially available, e.g. Lutensof XL from BASF SE.
• poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-carboxylic acid ester are preferably compounds of the formula
• R 6 is linear or branched C 8 -C 22 -alkyl
• R 7 is H or linear or branched CT-Cs alkyl
• q is a natural number from 1 to 50.
• r is 0 or is a natural number from 1 to 30, with the proviso that 2 ⁇ q + r ⁇ 50
• linear or branched C 8 -C 22 alkyl include, but are not limited to, n- octyl, /7-nonyl, /7-decyl, /7-undecyl, /7-dodecyl, /7-tridecyl, /7-tetradecyl, /7-pentadecyl, n- hexa- decyl, /7-heptadecyl, /7-octadecyl, /7-nonadecyl, /7-eicosyl, /7-heneicosyl, /7-docosyl, 2- ethylhexyl, 2-propyl-heptyl, 2-butyl-l-octyl, 2-pentyl-l-nonyl, isooctyl, isodecyl, isoundecyl, isododecyl, isotride
• linear or branched Cy-Cg alkyl include, but are not limited to, me thyl, ethyl, /7-propyl, /7-butyl, /7-pentyl, /7-hexyl, /7-heptyl, /7-octyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, t-butyl, 2-ethyl hexyl and isomers thereof.
• the poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-carboxylic acid esters have a molecular weight of from 300 to 2000 determined by ⁇ -N M R spectroscopy using for instance a 400 MHz spec trometer by Bruker.
• the molecular weight can be determined by the integration of the signals of the poly(C 2 -C 4 )alkylene glycol backbone and the comparison of this integral with the inte gral of the mono-(C 8 -C 22 )-alkyl signals.
• the alkoxylated oil is preferably an ethoxylated oil, more preferably ethoxylated derivative of castor oil with a hydrophilic/lipophilic balance of about 14 (H LB 14), such as Emulan ® EL.
• alkoxylated alkylamine are preferably compounds of the formula
• R is linear or branched, substituted or unsubstituted C 8 -C 22 -alkyl or linear or
• AO is, identical or different, selected from the group consisting of CH 2 -CH 2 -0,
• b is a natural number from 1 to 20, with the proviso that 2 ⁇ a + b ⁇ 40.
• a lkenyl covers acyclic unsaturated hydrocarbon residues, which may be linear or branched and unsubstituted or at least mono-substituted and comprise at least one double bond, preferably 1, 2 or 3 double bonds, with, as in the case of C 8 -C 22 alkenyl, 8 to 22 (i.e. 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22) carbon atoms.
• substituents may be se lected mutually independently from the group consisting of F, Cl, Br, I, -N0 2 , -CN, -OH, -SH, -N H 2 , -N (CH 3 ) 2 , -N (C 2 H 5 ) 2 and -N (CH 3 )(C 2 H 5 ).
• R is linear, unsubstituted C 8 -C 22 -alkenyl
• AO is CH 2 -CH 2 -0
• a is a natural number from 1 to 10
• b is a natural number from 1 to 10, with the proviso that 5 ⁇ a + b ⁇ 20.
• alkoxylated alkylamine is an ethoxylated alkylamine and most preferably oleyl amine ethoxylate.
• Suitable alkoxylated alkylamine are known and commercially available, e.g. LutensoT FA12 from BASF SE.
• the non-ionic surfactant is selected from alkyl polyethylene glycol ether, ethoxylated castor oil and oleyl amine ethoxylate.
• the presently claimed invention relates to a method for disinte grating the foundry mold comprising sand and a polyurethane binder comprising the step of (i) contacting the foundry mold with a composition comprising
• R x denotes linear or branched, unsubstituted or hydroxy substituted C 2 -C 22 al- kyl
• R 2 and R 3 independently of each other, denote H or linear or branched, unsubstituted or substituted C C 12 alkyl;
• AO is, identical or different, selected from the group consisting of CH 2 -CH 2 -0,
• x, y independently of one another are 0 or 1;
• the presently claimed invention relates to a method for dis integrating the foundry mold comprising sand and a polyurethane binder comprising the step of (0 contacting the foundry mold with a composition comprising
• Ri denotes linear or branched, unsubstituted or hydroxy substituted C 2 -C 22 alkyl
• R 2 and R 3 independently of each other, denote H or linear or branched, unsubstituted or substituted C C 12 alkyl;
• AO is, identical or different, selected from the group consisting of CH 2 -CH 2 -0, CH (CH 3 )-CH 2 -0, CH 2 -CH (CH 3 )-0, CH (C 2 H 5 )-CH-0, C(CH 3 ) 2 -CH 2 -0, CHC(CH 3 ) 2 -0 and CH 2 -CH (C 2 H 5 )-0, m is 1, 2, 3, 4, 5, 6 or 7, and x, y independently of one another are 0 or 1; and
• At least one non-ionic surfactant selected from the group consisting of poly(C 2 -C 4 )al- kylene glycol mono-(C 8 -C 22 )-alkyl ether, poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-car- boxylic acid ester, alkoxylated oil and alkoxylated alkylamine;
• the composition that is used according to the present invention does not contain water.
• water is added to the composition.
• the amount of water, if added to the composition is in the range of 0.1 wt.% to 12.0 wt. %, based on the total weight of the composition.
• the disintegration of the foundry mold takes a longer time, in the range of 100 minutes to 180 minutes when the composition comprises water, compared to the composition without water.
• the foundry mold may further comprise at least one additive.
• Additives are the materials generally added to the sand and binder mixture to develop some special property in the sand. Some commonly used additives for enhancing the properties of molding and core sands are coal dust, corn flour, dextrin, sea coal, pitch, wood flour, silica flour.
• Coal dust is added mainly for producing a reducing atmosphere during casting process.
• This reducing atmosphere results in any oxygen in the poles becoming chemically bound so that it cannot oxidize the metal. It is usually added in the molding sands for making molds for production of grey iron and malleable cast iron castings.
• Corn flour belongs to the starch family of carbohydrates and is used to increase the collaps- ibility of the molding and core sand. It is completely volatilized by heat in the sand mould, thereby leaving space between the sand grains. This allows free movement of sand grains, which finally gives rise to mould wall movement and decreases the mold expansion and hence defects in castings. Corn sand if added to molding sand and core sand improves significantly strength of the mold and core.
• Dextrin also belongs to starch family of carbohydrates that behaves also in a manner similar to that of the corn flour. Dextrin increases dry strength of the molds.
• Sea coal is the fine powdered bituminous coal which positions its place among the pores of the silica sand grains in molding sand and core sand.
• sea coal changes to coke which fills the pores and is unaffected by water. Because to this, the sand grains become restricted and cannot move into a dense packing pattern.
• sea coal reduces the mould wall movement and the permeability in mold and core sand and hence makes the mold and core surface clean and smooth.
• Pitch is distilled form of soft coal. It can be added from 0.02 % to 2% in mold and core sand. Pitch enhances hot strengths, surface finish on mold surfaces and behaves exactly in a man ner similar to that of sea coal.
• Wood flour is a fibrous material mixed with a granular material like sand. Wood flour is rela tively long thin fibers prevent the sand grains from making contact with one another wood flour can be added in between 0.05 % to 2% in mold and core sand. Wood flour volatilizes when heated, thus allowing the sand grains room to expand. Wood flour will increase mould wall movement and decrease expansion defects. Wood flour also increases col la psibil ity of both mold and core.
• Silica flour is called as pulverized silica. Pulverized silica can be easily added up to 3% which increases the hot strength and finish on the surfaces of the molds and cores. It also reduces metal penetration in the walls of the molds and cores.
• the presently claimed invention is directed to a composition
• a composition comprising
• the presently claimed invention is directed to a composition com prising
• the presently claimed invention is directed to a composition com prising
• glycol mono-(C 8 -C 22 )-alkyl ether poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-carboxylic acid ester, alkoxylated oil and alkoxylated alkylamine.
• the presently claimed invention is directed to the use of the composi tion comprising
• the presently claimed invention is directed to the use of the compo sition comprising
• the presently claimed invention is directed to the use of the compo sition comprising
• glycol mono-(C 8 -C 22 )-alkyl ether poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-carboxylic acid ester, alkoxylated oil and alkoxylated alkylamine;
• the presently claimed invention is directed to a method for disintegrat ing the foundry mold comprising sand and a polyurethane binder comprising the step of (i) contacting the foundry mold with a composition comprising
• the presently claimed invention is directed to a method for disintegrating the foundry mold comprising sand and a polyurethane binder comprising the step of (i) contacting the foundry mold with a composition comprising
• the presently claimed invention is directed to a method for disinte grating the foundry mold comprising sand and a polyurethane binder comprising the step of (i) contacting the foundry mold with a composition comprising
• At least one non-ionic surfactant selected from the group consisting of poly(C 2 - C 4 )alkylene glycol mono-(C 8 -C 22 )-alkyl ether, poly(C 2 -C 4 )alkylene glycol mono- (C 8 -C 22 )-carboxylic acid ester, alkoxylated oil and alkoxylated alkylamine;
• composition comprising (a) at least one carboxylic acid amide of general formula (I)
• R x denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl
• Ri denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl
• the presently claimed invention is directed to a composition com prising
• R x denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl
• glycol mono-(C 8 -C 22 )-alkyl ether poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-carboxylic acid ester, alkoxylated oil and alkoxylated alkylamine.
• the presently claimed invention is directed to the use of the composi tion comprising
• R x denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl; and (b) monoethanolamine,
• the presently claimed invention is directed to the use of the compo sition comprising
• R x denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl
• the presently claimed invention is directed to the use of the compo sition comprising
• R x denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl
• glycol mono-(C 8 -C 22 )-alkyl ether poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-carboxylic acid ester, alkoxylated oil and alkoxylated alkylamine;
• the presently claimed invention is directed to a method for disintegrat ing the foundry mold comprising sand and a polyurethane binder comprising the step of (i) contacting the foundry mold with a composition comprising
• Ri denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl
• the presently claimed invention is directed to a method for disintegrating the foundry mold comprising sand and a polyurethane binder comprising the step of (i) contacting the foundry mold with a composition comprising
• Ri denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl
• the presently claimed invention is directed to a method for disinte grating the foundry mold comprising sand and a polyurethane binder comprising the step of (i) contacting the foundry mold with a composition comprising
• R x denotes linear or branched, unsubstituted C 2 -C 12 alkyl
• R 2 and R 3 denote methyl
• the presently claimed invention relates to a method for disintegrating the foundry mold comprising sand and a polyurethane binder comprising the steps of
• R x denotes linear or branched, unsubstituted or hydroxy substituted C 2 -C 22 alkyl
• R 2 and R 3 independently of each other, denote H or linear or branched, unsubstituted or substituted C C 12 alkyl;
• AO is, identical or different, selected from the group consisting of CH 2 -CH 2 -0, CH (CH 3 )- CH 2 -0, CH 2 -CH (CH 3 )-0, CH (C 2 H 5 )-CH-0, C(CH 3 ) 2 -CH 2 -0, CHC(CH 3 ) 2 -0 and CH 2 -CH (C 2 H 5 )- 0
• x, y independently of one another are 0 or 1
• step (ii) separating the sand from the mixture obtained in step (i);
• step (iii) drying the sand obtained in step (ii).
• the sand is separated from the mixture of sand and polyurethane binder by one or more methods known in the art, namely reconditioning, thermal methods, dry methods etc. Recon ditioning merely contemplates that the used sand is passed over magnetic pulleys, through lump breakers and screens, and then aerated to remove fines.
• Thermal methods of treatment include a roasting furnace, a fluid bed furnace and a rotary kiln.
• the thermal calcine system subjects the sand to temperatures in the range of 1200° -1500° in the presence of excess oxygen, thereby removing carbonaceous additives.
• Dry method includes mechanical methods which comprise impacting sand grains to fracture the "shells" of old bonds from individual grains.
• the sand is dried by processes known to a person skilled in the art.
• the sand is passed through a fluid bed furnace. Hot sand is then passed through a cooling drum where the sand is subsequently cleaned and cooled to room temperature by means of cooling air.
• the sand obtained after drying is routinely screened and returned to the system for reuse. The sand can be recycled and reused in the foundry for making foundry molds for a number of cycles.
• Asphalt Concrete Substitution of up to 15% spent sand for conventional asphalt concrete fine aggregate.
• Compost Additive Bulking agent for composted yard waste, to produce topsoil or topsoil additive.
• the method of the present invention can be used for a variety of foundry molds with varied sand and binder composition.
• a method for disintegrating the foundry mold comprising sand and a polyurethane based binder comprising at least the step of
• Ri denotes linear or branched, unsubstituted or hydroxy substituted C 2 -
• R 2 and R 3 independently of each other, denote H or linear or branched, unsub stituted or substituted Ci-Ci 2 alkyl;
• AO is, identical or different, selected from the group consisting of
• x, y independently of one another are 0 or 1; to obtain a mixture of the sand and the polyurethane binder.
• sand is selected from the group consisting of natural silica sand, clay, green sand, quartz sand, chromite sand, olivine sand, special sands and zirconium sand.
• Ri is selected from the group consist ing of ethyl, /7-propyl, /7-butyl, /7-pentyl, /7-hexyl, /7-heptyl, /7-octyl, /7-nonyl, /7-decyl, n- undecyl, /7-dodecyl, /7-tridecyl, /7-tetradecyl, /7-pentadecyl, /7-hexadecyl, /7-heptadecyl, /7-octadecyl, /7-nonadecyl, /7-eicosyl, /7-heneicosyl, /7-docosyl, isopropyl, isobutyl, iso pentyl, isohexyl, isoheptyl, isooctyl, isononyl, iso
• R 2 and R 3 independently of each other, are selected from the group consisting of H, methyl, ethyl, /7-propyl, /7-butyl, /7-pentyl, /7-hexyl, /7-heptyl, /7-octyl, /7-nonyl, /7-decyl, /7-undecyl, /7-dodecyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl and /- butyl.
• R 2 and R 3 inde pendently of each other are selected from the group consisting of H, methyl, ethyl, n- propyl, /7-butyl, isopropyl, isobutyl and /-butyl.
• step (i) is achieved by immersing the foundry mold at a temperature in the range of > 10 to ⁇ 200 °C.
• step (i) is carried out for a time period of > 10 min. to ⁇ 60 min.
• step (iii) drying the sand obtained in step (ii).
• composition comprises at least one surfactant.
• non-ionic surfactant is selected from the group consisting of poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-alkyl ether, poly(C 2 -C 4 )alkylene glycol mono-(C 8 -C 22 )-carboxylic acid ester, alkoxylated oil and alkoxylated alkylamine.
• non-ionic surfactant is selected from alkyl polyethylene glycol ether, ethoxylated castor oil and oleyl amine ethoxylate.
• composition comprises water
• composition comprising
• composition according to embodiment 21 for disintegrating foundry mold.
• a method for disintegrating the foundry mold comprising sand and binder comprising the step of
• Lutensol ® FA12 (Oleylamine ethoxylate)
• Lutensol ® XL60 C 10 -Guerbet alcohol ethoxylates
• Emulan ® EL (Castor oil ethoxylate)
• Agnique ® AM D 810 (C 8 /C 10 fatty acid N ,N-Dimethylamide) are available from BASF SE, Ludwigshafen, Germany.
• Foundry mold sample of size 9 cm X 2.2 cm X 2.2 cm, made of PU-sand composite was pre pared according to state of the art.
• the foundry mold sample was immersed (one-third) in the composition as disclosed in Ex amples 1 to 6, at room temperature. The time of collapse of the sample was determined. The time of collapse is the time taken for the disintegration of the foundry mold sample completely resulting into the mixture of sand and binder.

Landscapes

• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Processing Of Solid Wastes (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Detergent Compositions (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=61868377

Family Applications (1)

Country Status (8)

Citations (5)

Family Cites Families (5)

• 2019
  • 2019-03-21 CN CN201980024473.6A patent/CN111936252A/zh active Pending
  • 2019-03-21 RU RU2020135681A patent/RU2020135681A/ru unknown
  • 2019-03-21 BR BR112020019796-3A patent/BR112020019796A2/pt not_active Application Discontinuation
  • 2019-03-21 EP EP19711120.6A patent/EP3774114A1/en active Pending
  • 2019-03-21 US US17/042,240 patent/US20210114090A1/en not_active Abandoned
  • 2019-03-21 JP JP2020552244A patent/JP2021519214A/ja active Pending
  • 2019-03-21 MX MX2020010276A patent/MX2020010276A/es unknown
  • 2019-03-21 WO PCT/EP2019/057042 patent/WO2019185437A1/en active Application Filing

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events