Patent GB-839185-A (GB)
Title: Improvements in or relating to the manufacture of cellular polymeric materials
Inventor: PACKER ERIC ARTHUR
IPC: C08G18/18
Filed: 1955-03-04
Abstract: Salts of tertiary amines with organic carboxylic or sulphonic acids may be made by mixing stoichiometric proportions of the ingredients in presence or absence of a solvent or diluent.  Salts may be isolated as crystalline solids.  Excess acid may be used and polybasic acids may yield the acid salts.  The salts may be formed in a mixture of materials used for making polyurethanes.  Amines mentioned are: triethylamine, N-ethylpiperidine, N : N - dimethylcyclohexylamine, triethanolamine, diethylaminoethanol, N - diethylaminoethyl benzamide, N - diethyl aminoethyl acetamide, di - (b  - diethylaminoethyl) - adipate, the di - (b  - diethylaminoethyl)-urethane of toluylene diisocyanate and pyridine. Acids mentioned are: oxalic, malonic, fumaric, maleic, glutaric, phthalic, isophthalic, terephthalic, formic, acetic, benzoic, salicylic, m- or p-hydroxybenzoic, hydroxy naphthoic, mono-, di- or tri-chloracetic, trifluoracetic, a -naphthalene sulphonic, citric, methacrylic and p-toluene sulphonic.ALSO:Cellular polymeric materials are made by the catalytic interaction of branched polyesters and organic polyisocyanates and, if desired, water (e.g. up to 10% by weight of the polyester), a salt of a tertiary amine with an organic carboxylic or sulphonic acid being used a catalyst.  For making rigid cellular materials the catalyst is a salt of a sulphonic or a monocarboxylic acid.  For resilient cellular materials, the polyester is one prepared from ingredients comprising 2-18 molar percentage based on the total dicarboxylic acid of at least one compound containing more than two isocyanate reactive groups, e.g. as described in Specification 790,420.  Suitable tertiary amines are triethylamine, N - ethylpiperidine, N,N1 - dimethylcyclohexylamine, triethanolamine, diethylaminoethanol, N - diethylaminoethyl benzamide, N - diethylaminoethyl acetamide, di - (b -diethylaminoethyl) adipate, and the di-(b -diethylaminoethyl) urethane of toluylene diisocyanate and pyridine.  Suitable organic acids for making the salts are oxalic, malonic, fumaric, maleic, glutaric, phthalic, isophthalic, terephthalic, formic, acetic, benzoic, salicyclic, m- or p-hydroxybenzoic, hydroxynaphthoic, monochloracetic, dichloracetic, trichloracetic, trifluoroacetic, a -naphthalene sulphonic, citric, methacrylic, and p-toluenesulphonic acids.  The salts may be made by mixing the amine and acid in stoichiometric proportions in presence or absence of a solvent or diluent.  The salt may be isolated or not before use.  Excess acid may be used and in the case of a polyfunctional acid the salt may be an acid one.  The salt may be formed by mixing the ingredients in situ in the reaction mixture.  Conventional additives may be included, e.g. pigments, fillers, flame-proofing materials such as 2-chloroethyl phosphate, extenders such as tricresyl phosphate, ground polyester scrap, structure modifiers such as polyorganosiloxanes, and emulsifying agents such as soaps or ethylene oxide condensates.  Blending of ingredients may be discontinuous or continuous as in Specification 839,183, and the ingredients may be mixed in any order.  In a typical example (1) a liquid polymer from diethylene glycol, adipic acid and hexanetriol (OH value 46.1 mg. KOH/gram; acid value 5.1 mg. KOH/gram; viscosity 122 poises at 25 DEG C.) is mixed with a mixture of 2.4 and 2.6 toluylene diisocyanates. Water, an octyl phenol-ethylene oxide condensate and the monochloroacetate of diethylaminoethanol are added.  A resilient cellular foam is obtained.  The products may be formed into supported or unsupported sheets by spreading on to fabric or metal, e.g. with a doctor knife. Specifications 553,733, 760,782, 839,187, and German Specification 901,471 also are referred to.ALSO:In the production of cellular polyurethanes by reacting branched polyesters and polyisocyanates possibly in the presence of water, the catalyst used is a salt of a tertiary amine with an organic carboxylic of sulphic acid.  The salt may be formed in situ in the reaction mixture. Sulphonic or monocarboxylic acid salts are used for rigid products. Specified polyesters are used for resilient products.  The specifications lists a large number of suitable salts.  Blending of ingredients may be in any order and may be discontinuous or continuous as in Specification 839,183.  The products may be formed into supported or unsupported sheets by spreading on to fabric or metal.