Patent GB-861056-A (GB)
Title: Blowing agent for foam materials
IPC: C08J9/10
Filed: 1957-06-06
Abstract: A process for producing foam materials comprises heating a composition comprising synthetic or natural rubber or a thermoplastic or thermosetting high-molecular weight polymer and a minor proportion of a compound of the formula <FORM:0861056/IV (a)/1> wherein Y represents an aliphatic or cycloaliphatic radical and Z represents an aliphatic, cycloaliphatic or aromatic radical, or wherein Y + Z taken together with the amino-nitrogen form a heterocyclic ring which may contain at least one further hetero atom comprising the amino-nitrogen of a second N,N-disubstituted-5-amino-1,2,3,4-thio-triazole group.  As materials to be foamed there are specified polyvinyl chloride, polyethylene, polystyrene, polyisobutylene, phenol-formaldehyde resins, ureaformaldehyde resins, natural rubber and polymerization products of conjugated diolefins such as butadiene, dimethylbutadiene, isoprene or copolymers thereof with polymerizable vinyl compounds such as styrene, a -methyl-styrene, acrylonitrile, methacrylonitrile, acrylates and methacrylates. When using natural or artificial rubber the process can be combined with vulcanization, the blowing agent supplying some of the sulphur.  Examples describe the production of foamed material by heating in a mould mixtures of (1) a polyvinyl chloride/dioctyl phthalate plastisol, sodium bicarbonate and 5-morpholyl-1,2,3,4-thiotriazole; (2) polyvinyl chloride, aromatic polyether plasticizer and N,N-dimethyl-5-amino-1,2,3,4-thiotriazole; (3) granulated polyethylene of molecular weight 20,000 to 25,000; (4) polystyrene and 5-morpholyl-1,2,3,4-thiotriazole; (5) liquid phenol-formaldehyde resin still containing free phenol and formaldehyde, 5-morpholyl-1,2,3,4-thiatriazole and p-toluene sulphonic acid; (6) pale crepe, zinc oxide, tetramethylthiuram disulphide, chalk, mineral oil, stearic acid, paraffin and N,N1 - dimethyl - N,N1 - bis - 1,2,3,4 - thiotriazolyl ethylene diamine; (7) butadieneacrylonitrile copolymer, zinc oxide, sulphur, tetramethyl thiuram disulphide, dibutyl phthalate, inactive carbon black, stearic acid, aldol-a naphthylamine and 5-morpholyl-1,2,3,4-thiotriazole; (8) butadiene-acrylonitrile copolymer, zinc oxide, sulphur, tetramethylthiuram disulphide, china clay, petroleum softener, stearic acid, paraffin and 5-dimethylamino-1,2,3,4-thiotriazole; (9) chloroprene rubber, china clay, dibutyl phthalate, active zinc oxide factis, active carbon black, 2-mercapto-5-methyl-tetrahydrotriazine-(1,3,5), magnesia and 5-dimethylamino-1,2,3,4-thiatriazole.ALSO:The invention comprises compounds of the general formula <FORM:0861056/IV (b)/1> p  wherein Y represents an aliphatic or cycloaliphatic radical and Z represents an aliphatic, cycloaliphatic or aromatic radical, or wherein Y + Z taken together with the amino-nitrogen form a heterocyclic ring, which may contain at least one further herero atom, which may comprise the amino-nitrogen of a second N,N-disubstituted 5 - amino - 1,2,3,4 - thia - triazole group. Such compounds can be prepared from secondary amines by conversion into the dithiocarbamic acid salts, the reaction of these with chloracetic acid to give the thiocarbaminoyl, thioglycollic acids, boiling of these compounds with hydrazine hydrate and nitrosation of the resulting disubstituted thiosemicarbazides.  In Examples: (1) 5-morpholyl-1,2,3,4-thiatriazole is prepared by treating morpholyl-thio-carbamic acid hydrazide at 5 DEG  to 10 DEG  C. with sodium nitrite and hydrochloric acid; (2) N,N - dimethyl - 5 - amino - 1,2,3,4 - thiatriazole is prepared analogously.  Also referred to are the corresponding 5 - dicyclohexylamino, 5-piperidyl and 5 - N - methyl - anilino - 1,2,3,4-thiatriazoles, N,N1-dimethyl-N,N1-bis - 1,2,3,4-thiatriazolyl - ethylenediamine and N,N1 - bis-1,2,3,4-thiatriazolylpiperazine.ALSO:A process for producing foam materials comprises heating a composition comprising synthetic or natural rubber or a thermoplastic or thermosetting high molecular weight polymer and a minor proportion of a compound of the formula: <FORM:0861056/V/1> wherein Y represents an aliphatic or cycloaliphatic radical and Z represents an aliphatic cycloaliphatic or armomatic radical or wherein Y + Z taken together with the amino-nitrogen form a heterocyclic ring, which may contain at least one further hetero atom which may comprise the amino-nitrogen of a second N, N-disubstituted-5-amino- 1, 2, 3, 4-thia-triazole group. As material to be foamed there are specified polyvinyl chloride, polyethylene, polystyrene, polisobutylene, phenol-formaldehyde resins, urea-formaldehyde resins, natural rubber and polymerisation products of conjugated diolefins such as butadiene, dimethylbutadiene, isoprene or copolymers thereof with polymerisable vinyl compounds such as styrene, a -methyl-styrene, acrylonitrile, methacrylonitrile, acrylates and methacrylates. When using natural or artificial rubber the process can be combined with vulcanisation, the blowing agent supplying some of the sulphur.  Examples described the production of foamed material by heating in a mould mixtures of (1) a polyvinyl chloride/dioctyl phthalate plastisol, sodium bicarbonate and 5-morpholyl-1, 2, 3, 4-thiatriazole; (2) polyvinyl chloride, aromatic polyether plasticizer and N, N-dimethyl-5-amino-1, 2, 3, 4-thiatriazole; (3) granulated polyethylene of molecular weight 20,000 to 25,000; (4) polystyrene and 5-morpholyl-1, 2, 3, 4-thiatriazole; (5) liquid phenolformaldehyde resin still containing free phenol and formaldehyde, 5-morpholyl-1, 2, 3, 4-thiatriazole and p-toluene sulphonic aicd; (6) pale crepe, zinc oxide, tetramethylthiruam disulphide, chalk, mineral oil, stearic acid, paraffin and N, N1-dimethyl-N, N1-bis-1, 2, 3, 4-thiatriazolyl ethylene diamine; (7) butadiene-acrylonitrile copolymer, zinc oxide, sulphur, tetramethyl thiuram disulphide, dibutyl phthalate, inactive carbon black, stearic acid, aldol a -naphthylamine and 5-morpholyl-1, 2, 3, 4-thiatriazole; (8) butadiene-acrylonitrile copolymer, zinc oxide, sulphur, tetramethylthiuram disulphide, china clay, petroleum softener, stearic acid, paraffin and 5-dimethylamino-1, 2, 3, 4-thiatriazole; (9) chloroprene rubber, china clay, dibutyl phthalate, active zinc oxide factis, active carbon black, 2-mercapto-5-methyl-tetrahydrotriazine- (1, 3, 5), magnesia and 5-dimethylamino-1, 2, 3, 4-thiatriazole.