Methods of manufacture of thermoplastic polymers
A method of manufacture of a polyetherimide copolymer composition includes contacting a substituted phthalic anhydride and 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. to provide a bis(phthalimide) composition comprising diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing solvents and a bis(phthalimide); and copolymerizing the bis(phthalimide), a substituted aromatic compound, and an alkali metal salt of a dihydroxy aromatic compound in the presence of diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing to form a polyetherimide copolymer. The method does not require any catalyst either for the imidization or the polymerization.
1. A method for the manufacture of a polyetherimide copolymer composition, the method comprising
contacting a substituted phthalic anhydride and an organic diamine in the presence of sulfolane 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 a bis(phthalimide) composition comprising sulfolane and a bis(phthalimide) of the formula
and
copolymerizing the bis(phthalimide), a substituted aromatic compound of the formula
and an alkali metal salt of a dihydroxy aromatic compound of the formula
MO—Z—OM
in the presence of sulfolane to form a polyetherimide copolymer comprising structural units of the formulas
wherein in the foregoing formulae
X, X 1 , and X 2 are each independently fluoro, chloro, bromo, iodo, nitro, or a combination comprising at least one of the foregoing;
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, and a divalent group of the formula
wherein Q 1 is —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;
M is an alkali metal;
Z is an aromatic C 6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing;
G is —C(O)— or —SO 2 —; and
m is 1 or 2.
2. The method of claim 1 , wherein the stoichiometric ratio of the substituted phthalic anhydride to the organic diamine is 1.95:1 to 2.05:1.
3. The method of claim 1 , wherein
weight
of
bis
(
phthalimide
)
weight
of
bis
(
phthalimide
)
+
weight
of
sulfolane
(
100
)
is 1 to 30%.
4. The method of claim 1 , comprising copolymerizing the bis(phthalimide), the substituted aromatic compound, and the alkali metal salt in the presence of an endcapping agent.
5. The method of claim 1 , further comprising adding a monofunctional reactant to the substituted phthalic anhydride, the organic diamine, or sulfolane.
6. The method of claim 1 , wherein the contacting is conducted at a temperature of 130° C. to 250° C.
7. The method of claim 1 , wherein the contacting is conducted in the absence of an imidization catalyst.
8. The method of claim 1 , wherein the polymerization or copolymerization is conducted in the absence of a polymerization catalyst.
9. The method of claim 1 , wherein the polymerization or copolymerization is conducted in the presence of a polymerization catalyst.
10. The method of claim 1 , wherein the polymerization or copolymerization is conducted at a temperature of 130° C. to 250° C.
11. The method of claim 1 , wherein X is chloro, X 1 and X 2 are each independently chloro or fluoro, m is 1, and R is m-phenylene, p-phenylene, an arylene ether, a 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. The method of claim 1 , wherein the dihydroxy aromatic compound comprises bisphenol A, hydroquinone, biphenol, resorcinol, or a combination comprising at least one of the foregoing.
13. The method of claim 1 , wherein the substituted aromatic compound is 4,4′-difluorobenzophenone, 4,4′-dichlorodiphenylsulfone, or a combination comprising at least one of the foregoing.
14. The method of claim 1 , wherein the alkali metal salt of a dihydroxy aromatic compound is dispersed in a solvent comprising ortho-dichlorobenzene, xylenes, toluene, diphenyl sulfone, sulfolane, or a combination comprising at least one of the foregoing.
15. The method of claim 1 , the method comprising:
contacting a substituted phthalic anhydride and an organic diamine in the presence of sulfolane 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 a bis(phthalimide) composition comprising sulfolane and a bis(phthalimide) of the formula
and
copolymerizing the bis(phthalimide), a substituted aromatic compound of the formula
and a disodium salt or a dipotassium salt of bisphenol A in the presence of sulfolane to form a polyetherimide copolymer comprising structural units of the formulas
wherein in the foregoing formulae
X is chloro;
X 1 and X 2 are each independently chloro, fluoro, bromo, iodo, or nitro;
R is m-phenylene, p-phenylene, p,p-diphenylether, or 4,4′-diphenylsulfone;
Z is
and
G is —C(O)— or —SO 2 —.
16. The method of claim 1 , wherein
weight
of
bis
(
phthalimide
)
weight
of
bis
(
phthalimide
)
+
weight
of
sulfolane
(
100
)
is 15 to 25%.
17. The method of claim 1 , wherein
weight
of
bis
(
phthalimide
)
weight
of
bis
(
phthalimide
)
+
weight
of
sulfolane
(
100
)
is 18 to 22%.
18. The method of claim 11 , wherein R is m-phenylene, p-phenylene, para, para-diphenyl ether, 4,4-diphenylsulfone, or a combination comprising at least one of the foregoing.