BINDING AGENT COMPOSITIONS

Abstract: Binding agent compositions for inorganic fillers or oxides containing a curable binder such as a hardenable resin, and a ureido-functional organosiiicon compound as described. Foundry sand compositions including bind­ ing agent compositions as described, sand and a cata­ lyst for the hardenable resin. Shaped products compris­ ing inorganic oxide particles, e.g., sand, a binding agent composition as described and catalyst for the hardenabie resin wherein the hardenable resin is in its hardened form. Novel ureido-functional organosilicon compounds having two hydrolyzable or hydroxy groups to the mol­ ecule and at least one ureido-functionai group in which the ureido group is connected to silicon by means of a group containing at least five carbon atoms.

Description: 3ACKGROtD OF THX INVENTTION 1. Field Of The Invention This invention relates to binding agent compositions having especially good shelf life which can be used with inorganic fillers or oxides, such as foundry sand, for the purpose of imparting improved strength to shapes, such as foundry molds or cores, made therefrom. The invention also relates to inorganic oxide compositions, such as foundry sand compositions, containing the inorganic oxide, the improved binding agent composition and catalysts for said binding agent. The invention also relates to certain novel ureidofunctional organosilicon compounds having use in binding agent compositions for foundry sands. 2. Description Of The Prior Art It is well known in the art that one can impart general improved strengths and increased humidity resistance to foundry cores by adding a silane compound to the resinous foundry binder used to form the cores. Foundry cores made with such resinous binders as phenolic/isocyanate systems, furan systems, oil modified polyol/polyisocyanate systems, phenolic resins and urea/phenolic resins have a tendency to lose strength and become weak upon exposure to humid conditions. As illustrated by U. S. Pats. 3,409,579 and 3,403,721, silane compounds have been added to such resinous binders to increase the humidity resistance and general strength of foundry cores made with these binders. Acuaous distersions of silane compounds have also been used as binders themselves (see U. S. Pat No. 3,093,494). It is known that aminoalkyl trialkoxysilanes, such as a8-aminopropyltrimethoxysilane, improve the adherence of thermosetting resins to inorganic oxide materials It is furthermore known that these aminosilanes can be mixed with thermosetting phenolic resins and then the resulting mixtures can be mixed directly with sands or other inorganic oxide material to be shaped and solidified (cf. DE-AS No. 1,252,853 and DE-PS No. 1,494,381). The use of N-(aminoalkyl)-aminoalkyisilanes as adhesion improvers between.thermosetting resins and inorganic oxide material is also known. These compounds are used in the same manner as the above-mentioned aminosilanes in which there is no substitution on the nitrogen atom (cf. U. S. Pat. No. 3,234,159). Both the aminoalkylsilanes which are not substituted on the nitrogen atom and those which are substituted by aminoalkyl groups, all of which are referred to hereinafter as aminosilanes, improve the adhesion of thermosetting phenolic resins to inorganic oxide substances to virtually the same degree when they are mixed with the resins. This improvement of adhesion, however, diminishes in the course of time if these aminosilane-containing resins are stored for a relatively long time at room temperature. U. S. Pat. No. 4,256,623 reports that, after standing for only 14 days, for example, the adhesion-improving action of aminosilanes declines by about 40t, and at the end of only a month the adhesivnz ng effect produced by \i'-aminopropyltriethoxy- silane in phenolic resin has been reduced by one half. It has been further reported that the loss of the adhesivizing action of the aminosilanes in mixture with thermosetting resins is probably due to a decomposition of these silanes in the resins. Therefore, there existed the problem of finding an adhesivizing agent which, when mixed with thermosetting resins, decomposes very slightly or not at all, and produces its adhesivizing action to the same or an only slightly lesser extent, even after the resin has been stored for a relatively long time and which therefore will be useful in the preparation of binding agents for inorganic oxide materials such as, for example, foundry sands, such binding agents being made from ureido-functional silanated phenolic resins whose strength enhancing effectiveness will remain unaltered or only slightly reduced, even after a relatively long period of storage. U. S. Pat. Nos. 3,671,562; 3,754,371 and 4,046,794 disclose ureido-functional organosilicon compounds and the use of same as coupling agents on inorganic substrates such as glass, clay, silica, hydrated silica, fumed silica, sand, e.g., foundry sand and the like. These patents fail to disclose or suggest the binding agent compositions or the foundry sand compositions disclosed and claimed herein and also fail to disclose or suggest the ureido-functional crganosilicon compounds claimed herein. In general, organofunctional silanes are widely used as additives to polymerizable resins to provide improved adhesion of the resin to substrates and to improve the physical properties of composites prepared from the resin and fibrous and/or particulate materials. A specific asplixation of this general use is the addition of orgacofunctional silicon compounds to hardenable resin compositions used as binders for sand to form molds and cores for use in casting metal articles. It is important in this use that the improvement in properties, provided by adding an organofunctional silicon compound, be stable in respect to the age of the organofunctional silicon compound/resin mixture. SUMMARY OF THE INVENTION This invention is concerned with the discovery that certain ureido-functional silicon compounds have novel and unexpected properties when employed as additives for the curable binder. It has been found, quite unexpectedly, that the use of ureido-functional silicon compounds that contain two hydrolyzable groups to the molecule provide significantly greater performance stability, when added to a curable binder, such as, a hardenable resin, than that provided by a corresponding ureido-functional silicon compound that contains three hydrolyzable groups Ureido-functional silicon compounds containing three hydrolyzable groups are useful additives for curable binders, such as, hardenable resins, and, in fact, are used commercially; however, the imvrove- ments in properties provided by the use of such compounds decrease with the time that the compound is in contact with the resin. The use of similar ureidofunctional silicon compounds, but having two hydrolyzable groups, pursuant to this invention, yield a significant increase in performance stability. More particularly, this invention relates to binding agent compositions for inorganic fillers or oxides comprising a curable binder such as a hardenable resin mixed with a ureido-functional organosilicon compound having: (a) at least one silicon-bonded ureido group of the formula (R'NC(O)R- (I) 2 n wherein R is an aliphatic radical containing nitrogen, hydrogen and at least three carbon atoms wherein at least one nitrogen atom therein is bonded to each [R'2NC(O)-] to form R2,NCONW at least one free valence of R'NCON 2 N is bonded to an alkylene carbon atom of R, any other free valence of R'NCON 2 is bonded to a member selected from the group consisting of hydrogen, alkyl, acryl, cycloalkyl and araLkyl, any nitrogen atom in R is separated from silicon by at least three sequentially joined carbon atoms, a is hydrogen, alkyl of 1 to 8 carbon atoms or a methylol group, preferably at least one R' group is hydrogen, most preferably both a' groups are hydrogen. (b) two silicon-bonded hydroxyl groups or hydrolyzable or condensible groups selected from the class consisting of alkoxy, acyloxy, aryloxy, amino and haloalkoxy; and (c) any remaining free valence of silicon being bonded (1) to oxygen which in turn is bonded to another silicon atom to form therewith a siloxane or (2), to hydrogen or, by carbon to silicon bonds, two a monovalent organic group selected from the group consisting of alkyl, acyl, cycloalkyl, aryl, alkaryl, aralkyl, aLkenyl, alkadienyl, cycloalkenyl, haloalkyl, halocycloalkyl, cyanoalkyl, cyanoaryl, cyanocycloalkyl, carboxyalkyl, carboxyaryl, carboxycycloalkyl, isocyanatoaryl, isocyana tocycloalkyl, alkyl carboxyaLkyl, aryl carboxyalkyl hydroxyalkyl, hydroxy (polyalkyleneoxy) alkyl, alkenoyloxyalkyl, epoxyalkyl, epoxyaLkyloxyalkyl, aminoaryl and aminoalkyl. The ureido-functional organosilicon compounds used in this invention preferably contain 1 to 10 silicon atoms. The novel ureido-functional organosilicon compounds of this invention are as described above wherein R as shown in formula I contains at least 5 carbon atoms. Preferably the ureido-functional organosilicon compound is a silane having the average formula: [(R'2NC(O)-R-]-Si (R n a '2.aX2 (11) wherein R, R' and n are as defined hereinabove, R" is hydrogen or a monovalent organic group bonded to silicon by a carbon to silicon bond, selected from the group consisting of alkyl, acyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, alkadienyl, cycloalkenyl, haloalkyl, halocycloalkyl, cyanoalkyl, cyanoaryl, cyanocycloalkyl, carboxyalkyl, carboxyaryl, carboxycycloalkyl, isocyanatoaryl, isocyanatocloalkyl, alkyl carboxyalkyl, aryl carboxyalkyl, hydroxyalkyl, hydroxy(polyalkyleneoxy)alkyl, alkenoyloxyalkyl, epoxyalkyl, epoxyalkyloxyalkyl, aminoaryl and aminoalkyl; X is hydroxyl or a hydrolyzable or condensible radical, selected from the group consisting of hydroxyl, alkoxy, acyloxy, aryloxy, amino and haloalkoxy; and a is an integer of 1 or 2. The novel ureido-functional organosilanes of this invention are those of formula II wherein R contains at least five carbon atoms. Specific examples of ureido-functional organosilanes are, NH2C(O)NH(CH2)2NH(CH2)3Si(Me) (OMe)2; NH2C(O)NHCH2CH(CH3) (CH2)2Si(Me) (OEt)2; NH2C(O)NH(CH2)2N[C(O)NH2](CH2)3Si (Me) (OMe)2; NH2C(O)NH(CH2)3Si (Et) OMe)2; MeO(Me)Si(CH2)3NHC(O)NH(CH2)3Si (Me) (OMe); NH2C(O)NHC2H4NHC2H4NHC3H6Si (Me) (OEt)2; NH2C(O)NH(CH2)2N[C(O)NH2](CH2)3Si (Et) (OMe)2; NH2C(O)NH(CH2)2N[C(O)NH2](CH2)2N[C(O)NH2](CH2)3Si(Et) (OEt) NH2C(O)NH(CH2)4SiEt(OMe)2; and NH2C(O)NH(CH2)4Si(C6H5) (OEt)2. included in the ureido-functional organosilicon compounds illustrated by formula I are relatively low molecular weight siloxanes, e.g., having 2 to 10 silicon atoms interconnected by silicon-bonded oxygen atoms forming 3DSiOSi- linkages. Ureido-functional organosiloxanes of this type have, Fer molecule, two silicon-bonded hydroxyl groups or two silicon-bonded hydrolyzable or condensible groups as defined above and at least one silicon-bonded group of the formula [R'NC(O)-R 2 n as defined in formula I and any remaining free valence of silicon is bonded to oxygen which in turn is bonded to another silicon atom to form therewith the siloxane, or, to hydrogen, or, by carbon to silicon bonds, to a monovalent organic group as defined above. The preferred ureido-functional organosiloxanes include the disiloxanes, trisiloxanes, tetrasiloxanes such as the cyclic tetramer, and the pentasiloxanes. Typical monovalent organic groups bonded to silicon in the ureido-functional organosilicon compounds described above including R" in the formula II include alkyl (e.g., methyl, ethyl, pentyl, dodecyl, octadecyl, 2 ethyihexyl, and the like), cycloalkyl (such as cyclobutyl, cyclohexyl, 4-methylcyclohexyl, and the like), aryl (such as phenyl, 2-naphthyl, 2-anthracyl, biphenyl, and the like), alkaryl (such as 4-methylphenyl, 2,4-diethylphenyl, 4-dodecylphenyl, and the like), araikyl (such as phenylethyl), aLkenyl (such as vinyl, allyl, 3-butenyl, oleyl, and the like), alkadienyl (such as l-butadienyl-l,4,l-. octadecatrienyl-9, 11, -13-, l-neoprenyl, and the like), cycloalkenyl (such as 3-cyclohexenyl), haloalkyl (such as chloromethyl, gamma-chloropropyl, 3, 3, 3-trifluoropropyl, perfluoropropyl, haloaryl (such as 4-chlorophenyl, 2,4dichlorophenyl, chloronaphthyl), halocycloalkyl (such as 4-chlorocyclohexyl), cyanoalkyl (such as beta-cyanoethyl, gamma-carboxypropyl and the like); cyanoaryl (such as 4-cyanophenyl); cyanocycloalkyl (such as 4-cyanocyclohexyl, 3-cyanocyclopentyl, and the like); carboxyalkyl (such as beta-carboxyethyl, gamma-carboxypropyl, and the like); carboxyaryl (such as 4-carboxyphenyl); carboxycycloalkyl (such as 4-carboxycyclohexyl, 3-carboxycyclopentyl, and the like; isocyanatoalkyl (such as gammaicocyanatopropyl, delta-isocyanatobutyl, and the like); isocyanatoaryl (such as 4-isocyanatophenyl); isocyanatocycloalkyl (such as 4-isocyanato-cyclohexyl); alkyl or aryl carboxyalkyl (such as betamethylcarboxyethyl, gammaphenyl carboxypropyl, and the like); hydroxyalkyl (such as hydroxymethyl, gamma-hydroxypropyl, and the like; hydroxy(polyalkyleneoxy)alkyl (such as omega-hydroxy (polyethyleneoxy)propyl, and the like); alkenoylcxyallcyl (such as gamma- acry lyoxypropyl, gamma-methacryloxypropyl, and the like; epoxyalkyl (such as 1,2-epoxyethyl, 1,2 epcxypropyl, l,2-epoxybuvyl, and the like; epoxy alkyloxyaLkyl (such as glycidyloxypropyl); epoxycycloalkyl (such as beta-3,4-epoxycyclbexylethal); aminoaryl and aminoalkyl (such as aminomethyl, gamma-aminopropyl, deltaaminobutyl, ?-aminochenyi, and the like); and the lie. Typical of the hydrolyzable or condensible groups bonded to silicon in the ureido-functional organosilicon compounds described above including X in formula II include for example alkoxy, e.g., methoxy, ethoxy, propoxy, dodecyloxy, isopropoxy, and the like; aryloxy, e.g., phenoxy, naphthyloxy, biphenyloxy, and the like; alkylamino and arylamino, such as methylamino, diethylamino, phenylamino, and the like; acyloxy, e.g., formyloxy, acetyloxy, propoxy, and the like; any organofunctional radicals such as hydroxyalkoxy, e.g., betahydroxyethoxy, gamma-hydroxypropoxy, and the like; hydroxy alkoxyalkoxy, such as beta-hydroxyethoxyethoxy, omegahydroxy (polyethyleneoxy)ethoxy, omega-hydroxy (poly-1,2propyleneoxy, and the like; cyanoalkoxy, such as betacyanoethoxy, beta-cyanchexoxy and the like; cyanoalkoxyalkoxy, such as beta-cyanoethoxyethoxy, omega-cyanoethoxy (polyethyleneoxy), omega-cyanoethoxy(poly-1,2-proyleneoxy) and the like; carboxyalkoxy, such as beta-carboxyethoxy, beta-carboxyhexoxy and the like; haloalkoxy,such as chloromethoxy, bromoethoxy perfluoropropoxy, and the like; and the like. The ureido-functional organosilicon compounds used in this invention can be produced by reacting an o rganocarbamate with an amino-functional organosilicon having: (a) at least one silicon-bonded group of the formula [R']-R- (III) n wherein R, R' and n are as defined in connection with formula I and each R'which is present n times in formula 111 is bonded to a nitrogen atom of R; (b) two silicon-bonded hydroxyl groups or hydrolyzable or condensible groups as defined hereinabove; and (c) any remaining free valence of silicon being bonded to (1) oxygen which in turn is bonded to another silicon atom to form therewith a siloxane, or (2) to hydrogen or, by carbon to silicon bonds to a monovalent organic group as described hereinabove. The amino-functional organosilicon compounds used to make the ureido-functional organosilicon compounds employed herein preferably contain 1 to 10 silicon atoms. The amino-functional organosilicon compounds used to make the novel ureido-functional organosilicon compounds of this invention are as described above wherein R as shown in formula TIT contains at least 5 carbon atoms. Suitable aminofunctional organosilicon compounds useful herein are disclosed in the prior art including USP 2,971,864, 2,832,754 and 2,942,019 and others, the disclosures of which are incorporated herein by reference. Additional specific examples are gamma aminopropylmethyldimethoxysilane, N-methyl-gammaaminopropylmethydimethoxylane, N-(gamma-aminopropyl)gamma-aminopropyömethyldimethoxysilanem N-(gamma-aminopropyl)-N-methyl-gamma-aminopropylmethyldimethoxysilane and gamma-aminopropylethyldiethoxysilane, and the like. Organocarbamates used to produce the ureido- functional organosilicon compounds used in this invention include alkyl, cycloalkyl or aryl carbamates illustrated by methyl carbamater, ethyl carbamate, and n-propyl carbamate, n-butyl carbamate, cyclohexylcarbamate phenyl carbamate, 4-methylphenyl carbamate, 4-dodecyl phenyl carbamate, biphenyl carbamate, and alkylene, cycloalkylene and arylene carbamate, such as ethylene dicarbamate, 1,4-butylene dicarbamate, 1,4-phenylene dicarbamate, 4,4'-bisphenylene dicarbamate, l,4,-cyclo- hexylene dicarbamate, anti the like The reaction can be carried out neat or in solution or dispersion using solvents or nonsolvents for the silane and/or the carbamate reactants. Type of solvents and nonsolvents include hydrocarbon solvents, ether solvents amide solvents, kctone solvents and the like, such as mineral spirits, hexane, n-nonane, benzene, toluene, xylene, methylethyl ketone, methylisobutyl ketone, diethylether, di-n-disopropyl ether, N,N,-dimethyl formamide, and the lir. The temperature of the reaction can be relatively I depending upon te reactivity of the carbamate and the amound of amine present in the reaction, usually temperatures in the range of about 40 C. to about 180 C. are satisfactory. Typically a temperature about SOOC. to about 150 C. is more desirable. This reaction can be operated under atmospheric or subatmospheric pressures. Superatmospheric pressures are employable but are not considered to operate as beneficially as subatmospheric and atmospheric pressures. The reaction product can be separated by distillation, crystallization, decantation, and the like, utilizing standard processing equipment and procedures. There are other alternative ways known in the art for producing the ureido-functional organosilicon compounds and any suitable procedure can be used. For example, the corresponding isocyanato functional organosilicon compound can be reacted with ammonia to produce the corresponding ureido-functional organosilicon compound. Also, alkylation or methylolation of one or both of the R' groups can be performed on the aminofunctional organosilicon compound in which both R' groups are hydrogen or on the ureido-functional organosilicon compound in which both R' groups are- hydrogen. This invention is primarily directed to improvements in foundry sands and foundry cores and molds made therefrom. The foundry sands useful in the present invention are conventional foundry sands such as silica sands having a high silica content, for example a silica content of,at least 30% by weight. Examples of such foundry sands are (l) white silica sands such as Wedron White Silica sand, (99.88 by weight silica), Ottawa White Silica sand (99.88 silica), Minnesota White Silica sand (98.5% silica); (2) lake sands, such as Port Crescent sand (95.0% silica) Manley 20KK sand (91.9% silica), Agent Lake sand (94.2t silica), Lake Shore sand (93.5 silica); and (3) bank sands such as Juniada Bank sand (90.2 silica). These foundry sands normally have a Grain Fineness Number (GFN) of about 50 to 90, as determined by the standard AFS method. Other inorganic oxides or fillers can be bound by the binding agents pursuant to this invention and they include any suitable fibrous or particulate inorganic substance. At the time of mixing the binding agent with the fillers, the fillers may be in the form of particles, spherical or approximately isometric, or they may be in the form or plates or needles (fibers). The size of the filler particles is not critical, any of the conventionally used fillers being suitable in this respect. Among the specific fillers which may be used in the present invention are asbestos, ground glass, kaolin and other clay minerals, silica, calcium silica, magnesium oxide, barium carbQnate,barium sulfate (barytes), metal fibers and powders, glass fibers, refractory fibers1 non-reinforcing carbon blacks, titanium dioxide, mica, talc, chopped glass, alumina, quartz, wollastonite (calcium silicate), and inorganic coloring pigments. The curable binders useful in the binding agent compositions of this invention-are polymerizable or thermosetting to form three-dimensional structures and are capable of binding the inorganic oxide or iller into a shaped mass. Included as examples of suitable curable binders are the foundry binders or hardenable resins which when used with the above ureido-functional silicon compounds of this invention show improved strength or resistance to humidity in the foundry core. Generally these foundry binders are the phenolic/polyisocyanate binder systems such as described in U. S. Pat. 3,409,579; furan binder systems such as described in U. S. Pat. 3,346,534; oil modified polyol/polyisocyanate binder systems such as described in U. S. Pat. 3,255,500; and phenolic and urea/phenolic resin binder systems such as described in U. S. Pats. 3,404,198 and 3,306,864. Further illustrative of resins which can be effectively bonded include the thermosetting resins, such as the phenol formaldehyde resins, melamineformaldehyde resins, alkyd resins, polyurethane resins, epoxy resins, and the like. It is quite surprising that cold-setting resins, such as phenol-formaldehyde resins, for example, which contain ureido-functional organosilicon compounds pursuant to this invention undergo little or no loss of their ability to adhere to fillers or inorganic oxide materials, the absolute adhesivity of these binding agents being equal to or in some cases even greater than that of conventional aminosilanes coupling agents. The stability of ureido-functional organosilicon compounds in cold setting-resins was unexpected and applies to those cases where none cr one or more or all of the hydrogen atoms of the ureido group H2NC(O)NH are substituted by an alkyl group or aryl group More broadly, the invention can be applied to substantially any polymeric material in which improved adhesion to fillers or inorganic oxides is desired, including, for example, any of the rubbers, resins or piastics with which fillers, e.g., inorganic oxides, are conventionally employed. Such polymers include natural rubber; synthetic rubbers such as styrenebutadiene rubber; ethylene-propylene terpolymer rubber; urethane rubbers; polyolefins such as polyethylene, polypropylene, and polyisobutylene; poly-acrylonitrile; polybutadiene; copolymers of butadiene and acrylonitrile; polystyrene; poly (styreneacrylonitrile); copolymers of styrene with butadiene and acrylonitrile; copolymers of ethylene with propylene or butene-l or vinyl acetate or maleic anhydride; polycarbonate resins; phenoxy resins, polyvinyl chloride; copolymers of vinyl chloride with vinyl acetate or other vinyl esters; polyvinyl acetate; linear polyesters; polyvinyl acetals; polyvinylidene chloride; copolymers of vinylidene chloride with vinyl chloride and acrylic acid; poly(methyl methacrylate); super-polyamides, e.g. nylon; polysulfones; allyl resins such as a polymer of diallyl phthalate; epoxy resins, phenolic resins; silicone resins; polyester resins including alkyd resins; poly(vinylacetate-vinyl chloride); poly(vinylidene chloride); thermoplastic polyurethanes; thermoplastic polyhydroxy ethers; thermoplastic polyesters; polyvinyl chlorde-ma7eic anhydrlde); and others. Preferred polymeric matrices are the thermosetting or curable resins, such as the hardenable foundry sand resins as described above, and the like. The proportions of ureido-functional organosilicon compound and curable binder in the novel binding agent compositions of this invention can be varied over a wide range. For example, the novel compositions can contain from about 0.01 to about 5, preferably about 0.05 to about 2, weight parts of ureido-functional organosilicon compound per 100 weight parts of curable binder. The proportions of binding agent composition and sand used in making the novel foundry sand compositions of this invention can be varied over a wide range and are generally the same respectively as the proportions of coupling agent and sand conventionally employed in the art. While the ureido-functional organosilicon compounds can be employed undiluted, it usually is more convenient to employ them as solutions, e.g., 25 to 95%, in suitable solvents such as methanol, ethanol, isopropanol and the like because such sclutions are easier to handle and disperse in the curable binder. DETALED DESCRIPTION OF THE INVENTION The following Examples are presented. The numbered Examples represent the present invention; the lettered Examples do not represent this invention and are for comparison purposes. Temperatures given are in OC, unless otherwise stated. The follwing designations used in the Examples and elsewhere herein have the following meanings: Me: methyl group lbs/inê or psi: pounds per square inch 0,69 N/cmê Et: ethyl group %: percent by weight unless otherwise specified wt %: weight percent cc: cubic centimeter gms: grams wt: weight parts: parts by weight unless otherwise indicated pts: parts by weight unless otherwise indicated EXAMPLE 1 Preparation of NH2C(O)NHC2H4NHC3H6Si(Me) (OMe)2 - Compound A Into a 250cc, 3-neck round bottom flask equipped with distillation head, mechanical stirrer, thermometer with thermo-watch and nitrogen armoschere, was charged 70.Ogrns NH2C2H4NHC3H6Si(Me) (OMe)2 (Compound B) plus 25.5gms methyl carbamate plus 0.lOgms dibutyl tin oxide. The reaction mixture was heated at 105 C. for about 15 hours. Amine titration was used to follow the extent of the reaction. The reaction was stopped at 93% completion. The product was stripped of methanol on a Rota-evaporator. The structure of the product as Compound A was confirmed by 13C nuclear magnetic resonance spectroscopy (NIGR). In addition to the structure given above for Compound A, 13C NIR suggested the formation of a small amount of cyclic structure. A 50 wt.% solution of the Compound A product in methanol was prepared. SAMPLE 2 Preparation of NH2C(O)NHCH2CH(CH3)C2E4Si(Me) (OEt)2 - Compound C Into a 250 cc, 3-neck round bottom flask equipped with distillation head, mechanical stirrer, thermometer with thermo-watch and nitrogen atmosphere, was charged 60.Ogms NH2CH2CH(Me)C2H4Si(Me) (GEt)2 (Compound D) plus 24.4gms ethyl carbamate plus 0.lOgms dibutyl tin oxide. The reaction mixture was heated at 1050C. for about 15 hours. Amine titer showed 93% completion. The product was stripped of ethanol on a Rota-evaporator. The stracture of the product as Compound C was confirmed by 13C nuclear magnetic resonance spectroscopy. A 50 wt. % solution of the product Compound C in methanol was prepared. Example 3 Preparation EMI20.1 Compound E Into a 250cc, 3-neck round bottom flask equipped with distillation head, mechanical stirrer, thermometer with thermo-watch and nitrogen atmosphere, was charged 70.0gms Compound B plus 51.Ogms methyl carbamate plus 0.l2gms dibutyl tin oxide. The reaction mixture was heated for about 15 hours at 105 0C. Amine titer showed 86% completion. The product was stripped of methanol on a Rota-evaporator. The product was an orange viscous liquid. A 50 wt. z product/methanol solution was prepared. The structure of the product as given above 13 for Compound E was confirmed by C NMR; however, there were 1 or 2 unidentifiable smaller amounts of by-products present. Examples 4-6, A and 3 Five foundry sand compositions were prepared containing the ingredients and amounts of same given in fable 1 below. In Examples 4,5 and 6, 0.19 milimole of Compound A, C and E, respectively, were used in the composition and in Example B, 0.l9 millimole of a commercial coupling agent, A-1160, having the formula NH2C(O)NHC3H6Si (OEt)3 was used. Example A was a control and no coupling agent was used. Table l Foundry Sand Formulation Ingredient Grams AFS Testing Sand 50-70 1500.00 Phenolic Binder* 27.90 Catalyst, Toluene Sulfonic 7.00 Acid H2O** 0.75/1.50 * 1.9% commodity resin based on sand weight. Resin is a commercial phenolic foundry resin supplied by Borden Chemical and identified as Thor F.B. 142 without silane coupling agent. 25% catalyst based on commodity resin. ** Due to extreme variation (35-95% RH) in humidity during these preparations, the formulations had to be adjusted accordingly. On dry days (c508 RH) 1.5gms H O was required and on humid days ( > 5uE ZI) 0.75 gms of H20 was required to ensure uniform processing parameters and consistent control values. In Examples B, 4, 5 and 6, 0.19 millimole of the silane coupling agent was added to the 27.9 grams of the phenolic binder and the resulting blend was stirred with a magnetic stirrer for 2 to 4 hours at room temperature. A portion of each resulting mixture was evaluated initially using the procedure described hereinafter and the remaining portion of each mixture was allowed to age for one month at room temperature and then evaluated. In evaluating each mixture of Examples 3, 4, 5 and 6 and in evaluating the control example x, 1500gms of sand were charged to the mixing bowl. While mixing at slow speed the required amounts of water and catalyst were added, separately, via syringe and mixed for two minutes The resin phenolicbinder (Example A) or phenolic binder/silane coupling agent mixture (Examples B, 4, 5 and 6) was added via syringe and mixing carried out for an additional two minutes. Immediately following completion of mixing, the molds were filled with the resulting sand mixtures, heaping full without compacting. The sand mixture was then pressed in firmly with the 414 rubber stopper. Additional sand mixture was then heaped, above the mold and smoothed off with a trowel. The resulting tensile specimens were allowed to stand for 24 hours after preparation and then tested. The tensile specimens were tested for tensile strength using a jig designed for testing briquets (ASTM C-190-63). The cross-head speed was 0.2 5 mm/min inches/minute. The tensile strengths, initially and after one month age, of the phenolic binder/silane coupling agent mixtures (Examples B, 4, 5 and 6) and the tensile strengths for the control (Example A) are given in Table 2 below. Table 2 Tensile Strength 2 (lbs/in2) N/cm EMI23.1 <tb> No. <SEP> CCcDlng <SEP> Assent <SEP> Initial <SEP> l- > bnts <SEP> Age <tb> A <SEP> Control <SEP> (no <SEP> coupling <SEP> acent) <SEP> :220)52 <SEP> :220) <SEP> 152 <tb> <SEP> 0 <tb> <SEP> II <tb> B <SEP> A-1160 <SEP> tE2C2EC3z5Si(OCzE5)3 <SEP> 495) <SEP> 2C3!215) <SEP> 148 <tb> 4 <SEP> Compound <SEP> A <SEP> Q90) <SEP> 2coy290) <SEP> 200 <tb> Ccmpound <SEP> C <SEP> (310) <SEP> 214285) <SEP> 197 <tb> 6 <SEP> Compound <SEP> E <SEP> (335)231 <SEP> yes5) <SEP> '37 <tb> The test results given in Table 2 prove the superior performance stability of each of the silane coupling agents of this invention, namely, Compounds A, C and E, as compared to the control (Example A) and the state-of-the-art silane coupling agent (Example B).

Claims: What is claimed is: 1. Novel organosilicon compound containing per molecule: (a) at least one silicon-bonded group of the formula /-R2'NC(O)-/n-R wherein R is an aliphatic radical containing nitrogen, hydrogen and at least five carbon atoms wherein t least one nitrogen atom, therein is bonded to each (R2NCO ' to form # R2'NCON # at least one free valence of R' NCON 2 is bonded to an alkylene carbon atom of R, any other free valence of # R2'NCON # is bonded to a member selected from the group consisting of hydrogen, alkyl, aryl, cycloalkvl and aralkyl, any nitrogen atom in R is separated from silicon by at least three sequentially joined carbon atoms, and n is at least one; (b) two silicon-bonded hydroxyl groups or hydrolyzable or condensible groups selected from the class consisting ot alkoxy, acyloxy, aryloxy, amino and haloalkoxy; and (c) any remaining free valence of silicon being bonded to (1) oxygen which in turn is bonded to another silicon atom to form therewith a siloxane or (2), by carbon to silicon bonds, to a monovalent organic group selected from the group consisting of alkyl, acyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, alkadienyl, cycloalkenyl, haloalkyl, halocycloalkyl, cyanoalkyl, cyanoaryl, cyanocycloalkyl, carboxyalkyl, carboya carboxycycloalkyl, isocyanatoaryl, isocyana tocycloalkyl, alkyl carboxyalkyl, aryl carboxyalkyl, bydroxyalkyl, hydroxy(polyalkyleneoxy) alkyl, alkenoyloxyalkyl, epoxyalkyl, epoxy alkylocyalkyl, aminoaryl and aminoalkyl or (3) to hydrogen. .2. Novel organosilicon compound as claimed in claim 1 wherein an average of at least on R' per group (a)-is hydrogen 3. Novel organosilicon compound as claimed in claim 2 wherein said organosilicon compound has the average formula: a#Si R"2-aX2 wherein R, R' and n are as defined in claim 9; R" is hydrogen or a monovalent organic group bonded to silicon by a carbon to silicon bond, selected from the group consisting of alkyl, acyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, alkadienyl, cycloalkenyl, haloalkyl-, halocycloalkyl, cyanoalkyl, cycanoaryl, cyanocycloalkyl, carboxyalkyl, carboxyaryl, carboxycycloalkyl, isocyanatoaryl, isocyanatocycloalkyl, alkyl carboxyalkyl, aryl carboxyalkyl, hydroxyalkl, hydroxy (polyalkyleneoxy)alkyl, alkenoyloxyalkyl, epoxyalkyl, epoxy alkyloxyalkyl, aminoaryl and aminoalkyl; X is hydroxyl or a hydrolyzable or condensible radical, selected' from the group consisting of hydroxyl, alkoxy, acyloxy, aryloxy, amino and haloalkoxy; ; and a is an integer of 1 or 2. 4. Novel organosilicon compound as claimed in claim .2 having the formula: H2NC(O)NHC2H4NHC3H6Si(Me) (OMe)2 or H2NC(O)NHCH2CH(Me)C2H4Si(Me) (OMe)2 or EMI27.1 5. In a binding agent composit4.on for inorganic oxides comprising a curable binder and an organosilicon compound coupling agent as claimed in claim 1 to 4. 6. Binding agent as claimed in claim 5 wherein said organosilicon compound is a siloxane having, per molecule, two silicon-bonded hydroxyl groups or two silicon-bonded hydrolyzable or condensible groups as defined in claim 1 and at least one silicon-bonded group of the formula [R'NC(o)-R- as defined in claim 1 2 n and any remaining free valence of silicon is bonded to oxygen which in turn is bonded to another silicon atom to form therewith the siloxane, or, by carbon to silicon bonds, a monovalent organic group as defined in claim 1. 7. Binding agent as claimed in claim 6 wherein said siloxane is a disiloxane, a trisiloxane, a tetra siloxane or a pentasiloxane or a cyclic tetrsiloxane. 8. Binding agent as claimed in claim 5 to 7 wherein said curable binder is a phenolic resin. 9. In a foundry sand composition containing foundry sand, a binding agent including a hardenable resin and an orgonosilicon con pound coupling agent as claimed in claim 5 and a catalyst for said hardenable resin. Clams wsL Austria Pat Is Claimed Is: 1. In a binding agent composition for inorganic oxides comprising a curable binder and an organosilicon compound coupling agent, the improvement wherein said organosilicon compound contains, per molecule (a) at least one silicon-bonded group of the formula [R'2NC(O)]n#R# wherein R is an aliphatic radical containing nitrogen, hydrogen and at least three carbon atoms wherein at least one nitrogen atom therein is bonded to each [R2'NCO)# to form 2 R'NCON 2 at least one free valence of R'NCON 2 is bonded to an alkylene carbon atom of R, any other free valence of R'NCON 2 is bonded to a member selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl and aralkyl, any nitrogen atom in R is separated from silicon by at least three sequentially joined carbon atoms; R' is hydrogen, aikyl having 1 to 8 carbon atons or methylol; and n is at least one; (b) two silicon-bonded hydroxyl groups or hydrolyzable or condesible groups selected from the class consisting of alkoxy, acyloxy, amino and haloalkoxy, and (c) any remaining free valence of silicon being bonded (l) to oxygen whicn in turn is bonded to another silicon atom to form therewith a siloxane or (2) to hydrogen or, by carbor to silicon bonds, to a monovalent organic group selected from the group consisting of alkyl, acyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, alkadienyl, cycloalkenyl, haloalkyl, halocycloalkyl, cyanoalkyl, cyanoaryl, cyanocycloalkyl, carboxyalkyl, carboxyaryl1 carboxycycloalkyl, isocyanatoaryl, isocyanatocycloalkyl, alkyl carboxyalkyl, aryl carboxyalkyl, hydroxyalkyl, hydroxy (polyalkyleneoxy)alkyl, alkenoyloxyalkyl, epoxyalkyl, epoxyalkyloxyalkyl, aminoaryl and aminoalkyl. 2. Binding agent as claimed in claim 1 wherein an average of at least one R' per group (a) is hydrogen. 3. Binding agent as claimed in claim 2 wherein said organosilicon compound has the average formula: [(R2'NC(O))n#R]aSi R"2-aX2 wherein R, 2' and n are as defined in claim l; R" is hydrogen or a'monovalent organic group bonded to silicon by a carbon to silicon bond, selected fro the group consisting of alkyl, acyl, cycloalkyl,- aryl, alkaryl, aralkyl, alkenyl, alkadienyl, cycloalkenyl, haloalkyl, halocycloalkyl, cyanoalkyl, cyanoaryl, cyanocycloalkyl, carboxyalkyl, carboxyaryl, carboxycycloalkyl, isocyanatoaryl, isocyanatocycloalkyl, alkyl carboxyalkyl, aryl carboxyalkyl, hydroxyalkyl, hydroxy(polyalkleneoxy)alkyl, alkenoyloxyalkyl, epoxyalkyl, epoxy alkyloxyalkyl, aminoaryl and aminoalkyl; X is hydroxyl or a hydrolyzable or condensible radical, selected from the group consisting of hydroxyl, alkoxy acyloxy, amino and haloalkoxy; and a is an integer of 1 or 2. 4. Binding agent as claimed in claim 2 wherein said organosilicon compound is a siloxane having, per molecule, two silicon-bonded hydroxyl groups or two silicon-bonded hydrolyzable or condesible groups as defined in claim 1 and at least one silicon-bonded group of the formula [R2'NC(O)]n#R# as defined in claim 1 and any remaining free valence of silicon is bonded to oxygen which in turn is bonded to another silicon atom to form therewith the siloxane, or, by carbon to silicon bonds, a monovalent organic group as defined in claim 1. 5. Binding anent as claimed in claim 4 wherein said siloxane is a disiloxane, a trisiloxane, a tetra siloxane or a pentasiloxane or a cyclic tetrasiloxane. 6. Binding agent as claimed ifl claim 2 wherein said organosilicon compound has the formula: H2NC(O)NHC2H4NH3H6Si(Me) (OMe)2 or H2NC(O)NHCH2CH(Me)C2H4Si(Me)(OEt)2 or EMI32.1 7. Binding agent as claimed in claim 2 wherein said curable binder is a phencllc resin 8. In a foundry sand composition containing foundry sand, a binding agent including a hardenable resin and an organosilicon comound coupling agent as claimed in claim 1 and a catalyst for said hardenable resin.

Inventors: MARSDEN, JAMES GLENN, PEPE, ENRICO JAMES
Applicants: UNION CARBIDE CORPORATION
Application year: 1982
Main classification: C07F7
IPC codes: C08L21, C08L33, C08K9, C08L77, B22C1, C08L51, C08L101, C07F7, C08L7, C08L27, C04B24, C08L23, C08L67, C08K5, C08L1