Fire retardant, thermosetting, resinous reaction products of phosphoric acid and methyol- or alkoxymethyl-substituted epoxides

Claim 1

The method of preparing a heat-curable, flame retardant resin which comprises: contacting a methylol- or alkoxymethyl-substituted epoxide, as defined below, with orthophosphoric acid (H 3 PO 4 ) mixed with 0 to 4 molecular proportions of water per molecular proportion of H 3 PO 4 , the amount of acid being such as to provide at least 0.7 P--OH hydroxyls per oxirane group, until essentially all of the oxirane groups originally present in said epoxide have been converted to glycol or phosphoester groups, said epoxide consisting essentially of molecules, each of which, independently, is of the formula ##STR31## wherein Y is H or a C 1 to C 4 alkyl or C 2 -C 4 alkenyl group, each YOCH 2 -- group is either ortho or para to a glycidyloxy group, x is 1, 2 or 3, c is 1 or 2 and d is 0 or 1; R 1 , independently in each occurrence, is H, methyl or ethyl; R 4 is Br, Cl, a C 1 -C 12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl or phenoxy group, a ##STR32## wherein, independently, in each of the latter two groups, Z is >C(CF 3 ) 2 , --SO 2 --, --S--, --O--, or a valence bond, R 1 is --H, --CH 3 or --C 2 H 5 , R 5 is a C 1 to C 12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenoxy, --Br or --Cl group, y and f are each 0, 1 or 2 and e is 0 or 1; and (x+f) is not greater than 4 and (x+y) is 2, 3 or 4; ##STR33## wherein s is 0 or 1 and p is 1, 2 or 3; R 6 is a C 1 to C 12 alkyl or a ##STR34## group, and R 1 and Y are defined as in formula (a), ##STR35## wherein Y, R 1 , R 4 , d and Z are as defined as in formula (a), v is 1, 2 or 3 and w, independently in each occurrence, is 0, 1 or 2, ##STR36## wherein, independently, in each occurrence R 1 is H, methyl or ethyl, X is H, --CH 2 OY, --Br, Cl or a C 1 -C 4 alkyl or alkenyl group, R 2 is --Br or --Cl, R 3 is methyl or ethyl, Y is H or a C 1 -C 4 alkyl or alkenyl group, a is 0, 1, 2, 3 or 4 and b is 0 or 1, ##STR37## wherein, J is H or a C 1 -C 10 alkyl or alkenyl group, Y is H or a C 1 -C 4 alkyl or alkenyl group, R 1 is H, methyl or ethyl X is H, --CH 2 OY, --Br, --Cl or a C 1 -C 4 alkyl or alkenyl group, independently in each occurrence, E is --CH 2 OY, --Br, --Cl or a C 1 -C 4 alkyl group, independently in each occurrence, and g is 0, 1 or 2, or (f) methylol substituted, oligomeric monoepoxides of the formula ##STR38## wherein u is 0, 1, 2 or 3, R 1 , independently in each occurrence, is H, methyl or ethyl and R 7 , independently in each occurrence, is a C 1 -C 12 alkyl, alkenyl, cycloalkyl, phenyl, phenalkyl or alkylphenyl group.

Claim 2

The method of preparing a heat-curable, flame retardant resin which comprises: contacting a methylol- or alkoxymethyl-substituted epoxide, as defined below, with orthophosphoric acid (H 3 PO 4 ) mixed with 0 to 4 molecular proportions of water per molecular proportion of H 3 PO 4 , the amount of acid being such as to provide at least 0.7 P--OH hydroxyls per oxirane group, until essentially all of the oxirane groups originally present in said epoxide have been converted to glycol or phosphoester groups, said epoxide consisting essentially of molecules, each of which, independently, is of the formula ##STR31## wherein Y is H or a C 1 to C 4 alkyl or C 2 -C 4 alkenyl group, each YOCH 2 -- group is either ortho or para to a glycidyloxy group, x is 1, 2 or 3, c is 1 or 2 and d is 0 or 1; R 1 , independently in each occurrence, is H, methyl or ethyl; R 4 is Br, Cl, a C 1 -C 12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl or phenoxy group, a ##STR32## wherein, independently, in each of the latter two groups, Z is >C(CF 3 ) 2 , --SO 2 --, --S--, --O--, or a valence bond, R 1 is --H, --CH 3 or --C 2 H 5 , R 5 is a C 1 to C 12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenoxy, --Br or --Cl group, y and f are each 0, 1 or 2 and e is 0 or 1; and (x+f) is not greater than 4 and (x+y) is 2, 3 or 4; ##STR33## wherein s is 0 or 1 and p is 1, 2 or 3; R 6 is a C 1 to C 12 alkyl or a ##STR34## group, and R 1 and Y are defined as in formula (a), ##STR35## wherein Y, R 1 , R 4 , d and Z are as defined as in formula (a), v is 1, 2 or 3 and w, independently in each occurrence, is 0, 1 or 2, ##STR36## wherein, independently, in each occurrence R 1 is H, methyl or ethyl, X is H, --CH 2 OY, --Br, Cl or a C 1 -C 4 alkyl or alkenyl group, R 2 is --Br or --Cl, R 3 is methyl or ethyl, Y is H or a C 1 -C 4 alkyl or alkenyl group, a is 0, 1, 2, 3 or 4 and b is 0 or 1, ##STR37## wherein, J is H or a C 1 -C 10 alkyl or alkenyl group, Y is H or a C 1 -C 4 alkyl or alkenyl group, R 1 is H, methyl or ethyl X is H, --CH 2 OY, --Br, --Cl or a C 1 -C 4 alkyl or alkenyl group, independently in each occurrence, E is --CH 2 OY, --Br, --Cl or a C 1 -C 4 alkyl group, independently in each occurrence, and g is 0, 1 or 2, or (f) methylol substituted, oligomeric monoepoxides of the formula ##STR38## wherein u is 0, 1, 2 or 3, R 1 , independently in each occurrence, is H, methyl or ethyl and R 7 , independently in each occurrence, is a C 1 -C 12 alkyl, alkenyl, cycloalkyl, phenyl, phenalkyl or alkylphenyl group.