Patent GB-990661-A (GB)
Title: Improvements in or relating to organosilicon ureas
IPC: C07F7/18
Filed: 1963-05-31
Abstract: The invention comprises silanes of the formula R1y(R11O)3- ySi-R-NZ-CO-NZ-R-Si (OR11)3- yR1y, where R1 is a hydrocarbon group of fewer than 7 C atoms, R11 is an acyl or alkyl group of fewer than 5 C atoms, or a group -(CH2CH2O)1 or 2-R111, where R111 is an alkyl group of fewer than 5 C atoms, y is 0, 1, 2 or 3, R is a divalent hydrocarbon group of fewer than 19 C atoms, free of aliphatic unsaturation, and joined to nitrogen through a non-aromatic C atom, and Z is hydrogen or an alkyl group of fewer than 7 C atoms, and the corresponding siloxanes and polymers thereof, and compositions containing these.  The silanes are prepared by heating at least 2 moles of a silane R1y(R11O)3- ySi-R-NHZ with 1 mole of urea.  A solvent, e.g. methanol, ethanol, isopropanol, or xylene may be used. The siloxanes or copolysiloxanes are obtained from the silanes by hydrolysis or co-hydrolysis with other silanes or by reaction with hydroxyterminated siloxanes in the presence of an amine catalyst. Copolymers containing 2-50% of the urea-containing units of the invention and 50-98% of dimethylsiloxane units are of particular value in making cellulosic fabrics water-repellent.  They are most effective when used in conjunction with a methyl- and hydrogen-containing siloxane in amount at least 5% of the total weight of siloxanes, and a creaseresistant resin, e.g. a urea-formaldehyde, alkylene - urea - formaldehyde, triazine - formaldehyde, triazone - formaldehyde, or pyrimidone-formaldehyde resin, or an epoxy resin, in amount 25-95.7% of the total weight. Compounds of this invention may also be copolymerized with aminoplast resins. The examples describe the preparations of [(C2H5O)3Si(CH2)3NH]CO, [(CH3O)3Si(CH2)3NH]2CO, and [(CH3O)3Si(CH2)3N(CH3)]2CO, and the urea derivatives of (CH3)3SiCH2CH(CH3)CH2NH2, (HCOO)2(C6H5)Si(CH2)18NH2, <FORM:0990661/C3/1> <FORM:0990661/C3/2> <FORM:0990661/C3/3> <FORM:0990661/C3/4> , and (C2H5COO)3SiC6H4NH2, and the hydrolysis of these.  The copolymerizations of [(CH3O)3Si (CH2)3NH]2CO with HO[Si(CH3)2O]12H, and of [CH3O(CH3)2Si(CH2)3NH]2CO with various other silanes and mixtures of silanes is described.  The former copolymer is emulsified with a methyl hydrogen polysiloxane, and a polyvinyl alcohol emulsifier, an ethylene-urea-formaldehyde resin, zinc nitrate, dibutyltin diacetate, zinc octoate, a toluene/tetrachlorethylene mixture and water. Alternative copolymers and aminoplasts are given, or diglycidyl ethylene glycol ether may be used as the crease-resistant resin.  Other uses:  adhesives, coatings, sizing agents for siliceous materials.ALSO:Cellulosic fabrics are rendered water repellent by treating them with silanes or siloxanes containing the structure <FORM:0990661/D1-D2/1> where R is a hydrocarbon group and Z is hydrogen or an alkyl group.  Preferred compounds are copolymers containing 2-50% by weight of units of the above type and 50-98% of methylsiloxane units, and these are most effective when used in conjunction with a methyl or methyl hydrogen polysiloxane, and a crease-resistant resin amounting to 25-97.5% of the total weight.  Examples of crease-resistant resins are urea-formaldehyde, alkylene urea-formaldehyde, triazine-formaldehyde, triazone-formaldehyde, pyrimidone-formaldehyde, and epoxide resins. An example describes the preparation of an emulsion containing a 40 : 60 mixture of a copolymer <FORM:0990661/D1-D2/2> and a trimethylsilyl-terminated methylhydrogen siloxane, a toluene-tetrachlorethylene solvent, a polyvinyl alcohol emulsifier, an ethylene ureaformaldehyde resin, zinc nitrate, dibutyltin diacetate, zinc octoate, and water.  This was applied to a cotton fabric, which was then dried and heated for 2 minutes at 177 DEG C., then tested for water repellancy after washing.  Other examples describe alternative procedures in which the urea-siloxane is uncopolymerized, and may be applied separately beforehand, or in which the urea-siloxane copolymer is applied separately beforehand, or in which other urea-containing units and other aminoplast resins, or an epoxy resin, are used.