Patent GB-971309-A (GB)
Title: New siloxanes
Inventor: IBBOTSON ARTHUR
IPC: C08G18/00
Filed: 1961-04-28
Abstract: The invention comprises siloxanes of general formula <FORM:0971309/C3/1> where m is at least 1, n=1, 2 or 3, R is a hydrocarbon group, R1 and R11 are each hydrocarbon groups or (OR111)mR1V, R111 is an alkylene group and R1V is alkoxy, cycloalkoxy, aralkoxy, aryloxy, acyloxy or acylamide group.  They are prepared by reacting a compound of general formula H(OR111)mR1V with a siloxane of formula <FORM:0971309/C3/2> wherein R is a hydrocarbon group and X is a hydrocarbon or a hydrogen atom in presence of a catalyst which is substantially neutral in reaction e.g. stannous octoate, dibutyltin dilaurate or lead octoate and a solvent e.g. benzene, toluene, xylene or chlorobenzene. R, R1 or R11 may be methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, cetyl, octadecyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl or 2-phenylethyl. R111 is either ethylene, trimethylene, 1:2 propylene, tetramethylene, 1:2 butylene or 2:3 butylene. R1V may be methoxy, ethoxy, propoxy, butoxy, octyloxy, octadecyloxy, cyclohemyloxy, benzyloxy, phenoxy, cresoxy, tertiary-butylphenoxy, octylcresoxy, benzoyloxy, benzmethylamido or butyryl methylamido. Groups (OR111)mR1V include the residues of alkylene and polyoxyalkylene glycol monoethers, e.g. monomethyl, ethyl, butyl, octyl, octadecyl, phenyl and benzyl ethers of ethylene, diethylene, triethylene, propylene, dipropylene, tripropylene, butylene, trimethylene, tetramethylene and higher polyethylene, polypropylene, polybutylene, polytrimethylene and polytetramethylene glycols. The group (OR111)mR1V may have a combination of oxyalkylene units, e.g. oxyethylene and oxypropylene units, and can also be (a) the residue of an alkylene or polyoxyalkylene glycol monoester, e.g. the monoacetate, monobutyrate, monoactoate or monobenzoate of the above glycols, or (b) an amido-alkoxy residue such as 2-(N-methyl-benzamido) ethoxy or 2-(N-methyl-acetamido) isopropoxy, or (c) a residue from higher molecular weight oxyalkylation derivatives of mono N-substituted carboxylic amides. The reaction temperature is 80 DEG -140 DEG C. Siloxanes prepared as above may be useful as surface active agents, mould release agents, hydraulic fluids and lubricants.  Polyurethane foams can be prepared from polyisocyanates and compounds containing at least 2 isocyanate-reactive groups (e.g. polyesters, polyesteramides, polyethers) and water and/or a low boiling liquid containing the above siloxanes in quantities of 0.05%-5% based on the weight of polyisocyanate-reactive compound. The polyesters and polyesteramides have a molecular weight of 200-5,000 with predominately OH end groups.  Polyethers used, of molecular weight 200-6000, include polymers or copolymers of cyclic oxides, e.g. ethylene oxide, epichlorhydrin, 1:2 propylene oxide, 1:2 butylene oxide, 2:3 butylene oxide, oxacyclobutane, substituted oxacyclobutanes and tetrahydrofuran; linear polyethers; glycols; and branched polyethers. Examples of suitable organic polyisocyanates include hexamethylene diisocyanate, tolylene 2:4 diisocyanate, tolylene 2:6 diisocyanate, diphenylmethane 4:41 diisocyanate, 3-methyldiphenyl methane 4:41 diisocyanate; m- and p-phenylene diisocyanate; chlorophenylene 2:4 diisocyanate, 4:41 diisocyanate 3:31 dimethyldiphenyl and diphenyl ether diisocyanate, naphthalene 1:5 diisocyanate, diphenyl 4:41 diisocyanate and cyclo-diisocyanates such as dicyclohexylmethane diisocyanate.  Other compounds specified are reaction products of excess diisocyanate and polyhydric alcohols; uretedione dimers and isocyanurate polymers of diisocyanates. Mixtures of polyisocyanurates may be used.  New boiling point liquids are monofluorotrichloromethane, dibromo-difluoromethane; 1:1:2 trichloro 1:2:2 trifluoroethane, dichlorodifluoromethane, dichloromonofluoromethane, dichlorotetrafluoroethane, monochlorodifluoromethane and difluoroethyl bromide or mixtures thereof, used 1-150% by weight of the hydroxylic polymer.  In addition 1-10% of water is used. A one stage or two stage process may be used. Other additives are flame-retarders, plasticizers, colouring matters, fillers and antioxidants. Examples 1, 4, 5 and 6 describe the preparation of siloxanes of the general formula where n=2, R is CH3, R1 and R11 are [OCH(CH3) CH2]m OC8H17 where m=4.88, R111 is CH2CH (CH3) and R1V is C8H17O and Examples 2, 3, 7 and 8 describe the preparation of foams therefrom. 3, 7 and 8 describe the preparation of foams therefrom.