METHODS OF MANUFACTURE OF BIS(PHTHALIMIDE)S
A method of manufacture of a bis(phthalimide) composition includes reacting, in the presence of molten diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing, a substituted phthalic anhydride with an organic diamine. The product mixture can be directly employed in the preparation of polyetherimides and other polyether polymers.
1 . A method for the manufacture of a bis(phthalimide) composition, the method comprising contacting a substituted phthalic anhydride with an organic diamine in the presence of diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents at a temperature of greater than 130° C.;
wherein the substituted phthalic anhydride has a formula
and the organic diamine has a formula
H 2 N—R—NH 2 ;
to provide the bis(phthalimide) composition comprising diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents, and a bis(phthalimide) of the formula
wherein, in the foregoing formulae,
X is fluoro, chloro, bromo, iodo, nitro, or a combination comprising at least one of the foregoing, and
R is an aromatic hydrocarbon group having 6 to 27 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a halogenated derivative thereof, a cycloalkylene group having 3 to 20 carbon atoms, a halogenated derivative thereof, —(C 6 H 10 ) z — wherein z is an integer from 1 to 4, an aromatic hydrocarbyl moiety having from 1 to 6 aromatic groups, a divalent group of the formula
wherein Q 1 is a single bond, —O—, —S—,
—C(O)—, —SO 2 —, —SO—, —C y H 2y wherein y is an integer from 1 to 5, or a combination comprising at least one of the foregoing,
wherein the stoichiometric molar ratio of the substituted phthalic anhydride to the organic diamine is 1.95:1 to 2.05:1.
2 . The method of claim 1 , wherein the stoichiometric molar ratio of the substituted phthalic anhydride to the organic diamine is 1.98:1 to 2.02:1.
3 . The method of claim 1 , wherein
weight
of
bis
(
phthalimide
)
weight
of
bis
(
phthalimide
)
+
weight
of
diphenyl
sulphone
or
sulfolane
(
100
)
is 1 to 30%.
4 . The method of claim 1 , further comprising
determining the stoichiometric molar ratio of the substituted phthalic anhydride to the organic diamine during the imidization of the substituted phthalic anhydride and the organic diamine; and
optionally adjusting the stoichiometric molar ratio by adding additional substituted phthalic anhydride or organic diamine.
5 . The method of claim 1 , further comprising heating the diphenyl sulfone to a temperature of greater than 130° C., and combining the substituted phthalic anhydride and the organic diamine with the heated diphenyl sulfone.
6 . The method of claim 1 , further comprising adding a monofunctional reactant to the substituted phthalic anhydride, the organic diamine, a solvent, or a combination comprising at least one of the foregoing, wherein the solvent comprises diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing.
7 . The method of claim 1 , wherein the contacting is conducted at a temperature of 130° C. to 250° C.
8 . The method of claim 1 , wherein the contacting is conducted in the absence of an imidization catalyst.
9 . The method of claim 1 , wherein the contacting is conducted in the presence of an imidization catalyst.
10 . The method of claim 1 , wherein
X is chloro, fluoro, bromo, or nitro, and
R is a divalent radical of the formula —(C 6 H 10 ) z — wherein z is an integer from 1 to 4,
or a combination comprising at least one of the foregoing, wherein Q 1 is a single bond, —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y — wherein y is an integer from 1 to 5, or a combination comprising at least one of the foregoing.
11 . The method of claim 1 , wherein X is chloro and R is m-phenylene, p-phenylene, diarylsulfone, a group of the formula
wherein Q 1 is a single bond, —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y wherein y is an integer from 1 to 5, or a combination comprising at least one of the foregoing.
12 . A method for the manufacture of a bis(phthalimide) composition, the method comprising contacting a substituted phthalic anhydride with an organic diamine in the presence of diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents at a temperature of 130° C. to 250° C.;
wherein
the substituted phthalic anhydride has a formula
and
the organic diamine has a formula
H 2 N—R—NH 2 ;
to provide the bis(phthalimide) composition comprising diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents and a bis(phthalimide) of the formula
wherein, in the foregoing formulae,
X is chloro, and
R is m-phenylene, p-phenylene, arylene ether, or diarylsulfone,
wherein the stoichiometric molar ratio of the substituted phthalic anhydride to the organic diamine is 1.98:1 to 2.02:1.
13 . The method of claim 12 , wherein
weight
of
bis
(
phthalimide
)
weight
of
bis
(
phthalimide
)
+
weight
of
diphenyl
sulphone
or
sulfolane
(
100
)
is 1 to 30%.
14 . The method of claim 12 , further comprising
determining the stoichiometric molar ratio of the substituted phthalic anhydride to the organic diamine during the imidization of the substituted phthalic anhydride and the organic diamine; and
optionally adjusting the stoichiometric molar ratio by adding additional substituted phthalic anhydride or organic diamine.
15 . The method of claim 12 , further comprising heating the diphenyl sulfone to a temperature of 130° C. to 250° C., and combining the substituted phthalic anhydride and the organic diamine with the heated diphenyl sulfone.
16 . The method of claim 12 , further comprising adding a monofunctional reactant to the substituted phthalic anhydride, the organic diamine, a solvent, or a combination comprising at least one of the foregoing, wherein the solvent comprises diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing.
17 . The method of claim 12 , wherein the contacting is conducted in the absence of an imidization catalyst.
18 . A bis(phthalimide) composition made by the method of claim 1 .
19 . A composition for manufacturing a bis(phthalimide) composition, comprising
a substituted phthalic anhydride and an organic diamine in diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents,
wherein the stoichiometric molar ratio of the substituted phthalic anhydride to the organic diamine is 1.95:1 to 2.05:1,
the substituted phthalic anhydride has a formula
and
the organic diamine has a formula
H 2 N—R—NH 2 ;
wherein, in the foregoing formulae,
X is fluoro, chloro, bromo, iodo, nitro, or a combination comprising at least one of the foregoing, and
R is an aromatic hydrocarbon group having 6 to 27 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a halogenated derivative thereof, a cycloalkylene group having 3 to 20 carbon atoms, a halogenated derivative thereof, —(C 6 H 10 ) z — wherein z is an integer from 1 to 4, an aromatic hydrocarbyl moiety having from 1 to 6 aromatic groups, a divalent group of the formula
wherein Q 1 is a single bond, —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y wherein y is an integer from 1 to 5, or a combination comprising at least one of the foregoing,
wherein the stoichiometric molar ratio of the substituted phthalic anhydride to the organic diamine is 1.98:1 to 2.02:1.
20 . A bis(phthalimide) composition comprising
diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents and a bis(phthalimide) of the formula
wherein,
X is fluoro, chloro, bromo, iodo, nitro, or a combination comprising at least one of the foregoing, and
R is an aromatic hydrocarbon group having 6 to 27 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a halogenated derivative thereof, a cycloalkylene group having 3 to 20 carbon atoms, a halogenated derivative thereof, —(C 6 H 10 ) z — wherein z is an integer from 1 to 4, an aromatic hydrocarbyl moiety having from 1 to 6 aromatic groups, a divalent group of the formula
wherein Q 1 is a single bond, —O—, —S—, —C(O)—, —SO 2 —, —SO—, —C y H 2y wherein y is an integer from 1 to 5, or a combination comprising at least one of the foregoing; and
wherein the solids content is 1 to 30%, calculated according to the following equation
weight
of
bis
(
phthalimide
)
weight
of
bis
(
phthalimide
)
+
weight
of
diphenyl
sulphone
or
sulfolane
.
(
100
)