Patent GB-891655-A (GB)
Title: Coating and adhesive compositions comprising polyisocyanato-aryl esters and amides of phosphoric and thiophosphoric acids
IPC: C07F9/12
Filed: 1959-02-27
Abstract: A coating or adhesive composition comprises an organic solvent solution of an isocyanatoaryl phosphorus compound of formula <FORM:0891655/III/1> where X is oxygen or sulphur, n is 0, 1 or 2, A represents a radical obtained by removing two active hydrogen atoms from a di-hydroxy-terminated polyester, polyether or alcohol; R is an unsubstituted or substituted O-aryl, O-aralkyl, O-alkaryl, O-cycloalkaryl, S-aryl, S-aralkyl, S-alkaryl, S-cycloalkaryl, N-(aryl)2, N-aryl-N-alkyl, N-(aralkyl)2, N-(alkaryl)2 or N-(cycloalkaryl)2; R1 and R1 are the same or different and may be the same groups as defined for R or may be unsubstituted or substituted O-alkyl, O-cycloalkyl, S-alkyl, S-cycloalkyl, N-(alkyl)2, N-(cycloalkyl)2, N-(cyclopentadienyl)2 O-vinyl, O- or S-cyclopentadienyl or chlorine; said compound also contains at least two aromatically bound isocyanate groups; substituents in the "R" groups may be halogen, alkoxy, carboxylic ester or unsaturated hydrocarbon groups.  The phosphorus compounds may be used in the form of adducts with polyhydric alcohols.  Suitable solvents include aromatic hydrocarbons, chlorinated hydrocarbons, ketones and esters. The compositions may also contain natural or synthetic rubbers, e.g. 5-30% rubber and 5-50% isocyanate.  The ratio of rubber to isocyanate may be from 10:1 to 1:10, preferably 3:1 to 1:3, e.g. 1:1.  In Example 3, a natural rubber composition containing fillers, vulcanizers and colouring matter is dissolved in benzine and mixed with a methylene chloride solution of tri-p-isocyanatophenyl phosphate and the resulting mixture applied by dipping, brushing or spraying to rubber articles and dried at room temperature. Specification 891,654 is referred to.ALSO:A natural or synthetic rubber composition used as a coating or adhesive composition comprises an isocyanato-aryl phosphorus compound of formula <FORM:0891655/IV (a)/1> where X is oxygen or sulphur, n is 0, 1 or 2, A represents a radical obtained by removing two active hydrogen atoms from a di-hydroxy-terminated polyester, polyether or alcohol; R is an unsubstituted or substituted O-aryl, O-aralkyl, O-alkaryl, O-cycloalkaryl, S-aryl, S-aralkyl, S-alkaryl, S-cycloalkaryl, N-(aryl)2, N-aryl-N-alkyl, N-(aralkyl)2, N-(alkaryl)2 or N-(cycloalkaryl)2; R1 and R1 are the same or different and may be the same groups as defined for R or may be unsubstituted or substituted O-alkyl, O-cycloalkyl, S-alkyl, S-cycloalkyl, N-(alkyl)2, N-(cycloalkyl)2, N-(cyclopentadienyl)2 O-vinyl, O- or S-cyclopentadienyl or chlorine; said compound also contains at least two aromatically bound isocyanate groups; substituents in the "R" groups may be halogen, alkoxy, carboxylic ester or unsaturated hydrocarbon groups.  The phosphorus compounds may be used in the form of adducts with polyhydric alcohols.  Suitable solvents present include aromatic hydrocarbons, chlorinated hydrocarbons, ketones and esters.  The compositions may contain 5-30% rubber and 5-50% isocyanate.  The ratio of rubber to isocyanate may be from 10:1 to 1:10, preferably 3:1 to 1:3, e.g. 1:1.  Specified synthetic rubbers are butyl rubber, butadiene-styrene rubber, butadieneacrylonitrile rubber and polymers of 2-chlorobuta-1,3-diene.  The usual vulcanizing composition ingredients may be present.  Specification 891,654 is referred to.ALSO:Isocyanatoaryl phosphorus compounds of formula <FORM:0891655/IV (b)/1> where X is oxygen or sulphur, n is 0, 1 or 2, A represents a radical obtained by removing two active hydrogen atoms from a di-hydroxy-terminated polyester, polyether or alcohol; R is an unsubstituted or substituted O-aryl, O-aralkyl, O-alkaryl, O-cycloalkaryl, S-aryl, S-aralkyl, S-alkaryl, S-cycloalkaryl, N-(aryl)2, N-aryl-N-alkyl, N-(aralkyl)2, N-(alkaryl)2 or N-(cycloalkaryl)2; R1 and R11 are the same or different and may be the same groups as defined for R or may be unsubstituted or substituted O-alkyl, O-cycloalkyl, S-alkyl, S-cycloalkyl, N-(alkyl)2, N-(cycloalkyl)2, N-(cyclopentadienyl)2, O-vinyl, O- or S-cyclo pentadienyl or chlorine and said compound also contains at least two aromatically bound isocyanate groups and substituents in the "R" groups may be halogen, alkoxy, carboxylic ester or unsaturated hydrocarbon groups, used in coating and adhesive compounds (see Groups III, IV(a) and VIII) may be prepared by phosgenating the corresponding aminoaryl compounds as described in Specification 891,654.  Reference is also made to adducts of the above compounds with polyhydric alcohols.  Specified compounds outside the scope of those claimed in Specification 891,654 are di-p-iso-cyanatophenyl phosphochloridate, di-p-isocyanatophenyl phosphor-N,N-dicyclopentadienylamidate and dicyclopentadienyl dithiophosphor - N,N - bis (4 - isocyanatophenyl) amidate.