Patent GB-928241-A (GB)
Title: Intermediates and polyurethane plastics
IPC: C07H15/08
Filed: 1961-03-01
Abstract: An addition product of an invert sugar and an alkylene oxide is used, with or without the addition of other active-hydrogen-containing compounds, to prepare polyurethanes (see Group IV(a)).  The products are said to be useful in making lacquers and coatings.  Coating compositions are produced by dissolving the sugar-alkylene oxide adduct, together with a polyisocyanate or blocked polyisocyanate (including prepolymers containing -NCO groups made from polyisocyanates and active hydrogen-containing compounds), in an organic solvent, e.g. xylene, ethyl acetate, toluene, ethylene glycol, or ethylene glycol monoethyl ether acetate.  The compositions may be applied by, e.g. dipping, brushing, rolling or spraying to, e.g. wood, metal, glass or paper.  In Example 6, 16,2 parts of a polyether (prepared from 3480 parts of propylene oxide and cu. 1000 parts of the invert sugar from cane sugar) are mixed with 31,8 parts of a 75% solution in ethyl acetate of an adduct, having an -NCO content of 13,2%, prepared from 1,1,1-trimethylol propane and toluylene diisocyanate.  This mixture is coated on a glass plate and hardens in 2 hours at about 60 DEG C.  Specifications 804,369 and 819,384 are referred to.ALSO:The reaction product from an invert sugar and an alkylene oxide is used as an intermediate for preparing polyurethanes.  The invert sugar is prepared by acid hydrolysis of oligosaccharides, e.g. malt sugar, cellobiose, trehalose, lactose, raffinose or preferably cane sugar.  The invert sugar may be mixed with up to 50% of other reactive compounds, e.g. alcohols, phenols, amines, lower polyethers and polyesters, before reaction with the alkylene oxide.  Suitable alkylene oxides are: ethylene, propylene, butylene, amylene, styrene, and phenoxy propylene oxides; epichlorohydrin; and 1-allyloxy2,3-epoxy propane. Propylene oxide is preferred.  The alkoxylation is carried out in the presence of 0,01 to 3% by weight of alkali, e.g. KOH, NaOH, NaOCH3, K2CO3, trimethyl or triethyl amine, or benzyl trimethyl ammonium hydroxide, preferably at 100 DEG -200 DEG C.  5-95% based on the product is the normal proportion of alkylene oxide, and the product should have a hydroxyl number of about 30-1,000, preferably 150-750.  The product is reacted with organic polyisocyanates, with or without the addition of crosslinking agents.  Isocyanates specified are: tetraand hexa-methylene diisocyanates; phenylene, naphthylene, diphenyl methane, toluylene, and di- and tri-isopropyl benzenes, diisocyanates; triphenylmethane triisocyanates; tri-(p-isocyanatophenyl) esters of phosphoric and thiophosphoric acids; 1-(isocyanatophenyl)-ethyl isocyanate; xylylene diisocyanates; derivatives of the above carrying alkoxy or aryloxy (e.g. OCH3, OC6H5) or NO2 groups or Cl; furfurylidene diisocyanates; reaction products of the above with less than equivalent quantities of plyhydroxy compounds, e.g. 1,1,1-trimethylolpropane, hexantriol, glycerol and butanediol; masked or polymerized polyisocyanates. Other active-hydrogen-containing compounds may be present, e.g. hydroxy polyesters, polyesteramides, polyethers and polythioethers; the preferred molecular weight of these is 500-10,000, hydroxyl numbers are preferably 50-350, and acid numbers below 5.  The sugar-alkylene oxide adducts may be reacted with excess isocyanate to yield prepolymers which may be reacted with a cross-linking agent, e.g. water, polyhydric alcohol, polyamine or amino alcohol, or with more of the adduct.  Alternatively, a hydroxyl-group-containing pre-polymer may be reacted with, e.g. organic peroxide, sulphur or formaldehyde.  Various additives may be present.  Lists of suitable acids, alcohols, amines &c. for the various stages are given.  The polyurethanes may be used to produce films, lacquers (see Group III), coatings, adhesives, solid or porous (see Group V) masses.  In the preparation of foams, a catalyst is preferably added, e.g. tertiary amines (many listed); molybdenum glycolate; tin compounds, e.g. SnCl2, dialkyl tin dicarboxylates and tin alcoholates; and organometallic compounds disclosed in U.S.A.  Specification 2,846,408.  Specifications 804,369 and 819,384 also are referred to.ALSO:Invert sugars are prepared from, e.g. malt sugar, cellobiose, trehalose, lactose, raffinose or preferably cane sugar, by treatment in the presence of normally 10-100%, by weight of sugar, of water and an organic, inorganic or Lewis acid, or an acidic ion exchanger (e.g. polystyrene sulphonic acids).  The water content is reduced to below 1%, and the sugar may be mixed with 0-50% of its weight of, e.g. alcohols, phenols, amines, lower polyethers or polyesters, and is then reacted with 5-95% of an alkylene oxide (based on the weight of the product), in the presence of 0.01 to 3% by weight based on sugar of a base. Suitable alkylene oxides are: ethylene, propylene, butylene, amylene, styrene or phenoxy propylene oxides; epichlorohydrin; 1-allyloxy-2,3-epoxy propane.  Suitable bases are: KOH, NaOH, NaOCH3.  K2CO3, trimethyl amine, triethyl amine, and benzyl trimethyl ammonium hydroxide.  Temperatures of 100-200 DEG C. are preferred.  The products should have a hydroxyl number of 30-1000, preferably 150-750.  In Example 1, cane sugar is heated 4 hours at 90 DEG C. in the presence of HBF4 and the product dehydrated, then reacted with propylene oxide in the presence of KOH at about 140 DEG C.  A similar process using betene-1-oxide is described in Example 8.  Specifications 804,369 and 819,384 are referred to.ALSO:Polyurethanes may be prepared from the adduct of an invert sugar and alkylene oxide by reaction with polyisocyanates with or without the addition of other, cross-linking compounds (see also Group IV(a)) in the form of a foamed product, if blowing agents, e.g. water, halohydrocarbons (CFU3, CF2U2) azo compounds (diazoaminohenzene), volatile hydrocarbons (portion) are added.  A propolymer containing excess isocyanate groups may be reacted with water, or water may be added to the isocyanate with the sugar-alkylene oxide adduct.  Colouring agents, fillers, emulsifiers (sulphonated castor oil), foam stabilisers (silicone oil, e.g. polydimethysiloxane; alkylsilane polyoxyalkylene block copolymers e.g. those of Specification 804,369) may be added. Preferably a catalyst is added, e.g. tertiary amine (many listed), molybdenum glycolate, SnU3, dialkyl tin dicarboxylates, tin alcoholates, organometallic compounds disclosed in U.S.A. Specification 2,846,408. In an Example 2, 100 parts of a polyether (from 1500 parts propylene oxide and/or 1000 parts of p  invert sugar from sucrose), 1 part N-methyl-N1-dimethylaminoethyl piperazine, 0,3 part dibutyl tin dilaurate, 0,3 part of C2H5-Si -[-O-(Si(CH3)2- O)6-(-CnH2nO) 30 C4H9]3 (where (CnH2nO)30 signifies a block copolymer of ethylene and propylene oxides) and 4 parts of 50% aqueous sodium castor oil sulphate were foamed by adding 181 parts of 4, 41-diisocyanatodiphenyl methane.  The same procedure is used in Examples 3, 4, 5 and 8.  Specification 819,384 also is referred to.