Methods for the manufacture of polyetherimides and polyetherimides made by the method
A method of manufacturing an isolated polyetherimide composition includes combining an as-synthesized polyetherimide comprising units of the formula (I) and a melt-stabilizing amount of a tri(C 8-30 acyl) glyceride, an anhydride of the formula (II), or a combination comprising at least one of the foregoing, to provide a mixture; and isolating a polyetherimide composition from the mixture to provide the isolated polyetherimide composition having a change in complex viscosity measured over 30 minutes at 390° C., at a shear rate of 6.28 rad/seconds, strain=5%, and under nitrogen, from +15 to −20%, preferably from +10 to −20%, more preferably from +5 to −20%.
1. A method of manufacturing an isolated polyetherimide composition, the method comprising
combining an as-synthesized polyetherimide comprising units of the formula
and a melt-stabilizing amount of
a tri(C 8-30 acyl) glyceride,
an anhydride of the formula
or a combination thereof,
wherein the melt stabilizing amount is 10 to 2,600 parts per million of anhydride equivalents, based on the total weight of the as-synthesized polyetherimide,
wherein in the foregoing formulas,
R is a substituted or unsubstituted C 6-30 aromatic hydrocarbon group, a substituted or unsubstituted, straight or branched chain C 4-30 alkylene group, a substituted or unsubstituted C 3-8 cycloalkylene group, or a combination thereof;
Z is an aromatic C 6-30 monocyclic or polycyclic group optionally substituted with 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, and
G is a hydrogen atom, a halogen atom, a nitro group, C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl, C 1-12 haloalkyl, C 1-12 alkoxy, C 1-12 haloalkoxy, C 3-12 cycloalkyl, C 5-12 cycloalkenyl, C 6-18 aryl, C 7-31 arylalkylene, C 7-31 alkylarylene, C 4-12 heterocycloalkyl, C 3-18 heteroaryl, C 1-12 alkyl sulfonyl, C 6-12 arylsulfonyl, tosyl, or a group of the formulas
wherein
T is —O—Z—O—, a single bond, —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R a )(═O)—wherein R a is C 1-8 alkyl or C 6-12 aryl, NR b wherein R b is a hydrogen atom, C 1-8 alkyl, or C 6-12 aryl, or T is a C 1-18 organic bridging group, and
X is chloro, bromo, iodo, or nitro, or a combination thereof, to provide a mixture; and
melt extruding the mixture to provide the isolated polyetherimide composition having
a change in complex viscosity measured over 30 minutes at 390° C., at a shear rate of 6.28 rad/seconds, strain=5%, and under nitrogen, from +15 to −20%; and
0 to 3,000 parts per million, based on a total weight of the isolated polyetherimide composition, of a dianhydride of the formula
2. The method of claim 1 , wherein each R is independently a divalent group of the formulae
wherein Q 1 is —O—, —S—, —C(O)—, —S(O) 2 —, —S(O)—, —P(R e )(═O)— wherein R e is a C 1-8 alkyl or C 6-12 aryl, —C y H 2y — wherein y is an integer from 1 to 5 or a halogenated derivative thereof, or —(C 6 H 10 ) z — wherein z is an integer from 1 to 4; and
each Z is independently a group of the formula
wherein
R a and R b are each independently a halogen atom or a monovalent C 1-6 alkyl group;
p and q are each independently integers from 0 to 4;
c is an integer from 0 to 4; and
X a is a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, or a C 1-18 organic bridging group.
3. The method of claim 1 , wherein the melt-stabilizing amount of the tri(C 8-30 acyl) glyceride, the anhydride, or the combination thereof is 10 to 1,600 parts per million of anhydride equivalents, based on the total weight of the as-synthesized polyetherimide.
4. The method of claim 1 , comprising the tri(C 8-30 acyl) glyceride, wherein the tri(C 8-30 acyl) glyceride is of the formula
wherein each R 1 , R 2 , and R 3 is independently a substituted or unsubstituted C 8-30 alkyl group, optionally having 0 to 6 unsaturations.
5. The method of claim 4 , wherein each R 1 , R 2 , and R 3 is independently a C 8-30 alkyl group having 0 to 2 unsaturations and optionally substituted with one or more halogens.
6. The method of claim 5 , wherein the tri(C 8-30 acyl) glyceride comprises glycerol tristearate.
7. The method of claim 1 , comprising the anhydride, wherein G is a group of the formula
optionally wherein Z in the group G is not the same as Z in the as-synthesized polyetherimide.
8. The method of claim 1 , wherein G is a group of the formula
wherein R a and R b are each independently the same or different, and are a halogen atom or a monovalent C 1-6 alkyl group; p and q are each independently integers of 0 to 4; c is 0 to 4; and X a is a C 1-18 bridging group; and
optionally wherein Z in the group G is not the same as Z in the as-synthesized polyetherimide.
9. The method of claim 1 , comprising the anhydride, wherein the anhydride is of the formula
wherein X is a hydrogen atom, halogen atom, or a nitro group.
10. The method of claim 1 , comprising the anhydride, wherein the anhydride is of the formula
wherein Z in the anhydride is the same as Z in the as-synthesized polyetherimide; or
the anhydride is of the formula
wherein R a and R b are each independently the same or different, and are a halogen atom or a monovalent C 1-6 alkyl group; p and q are each independently integers of 0 to 4; c is 0 to 4; X a is a C 1-18 bridging group; and R a , R b , p, q, c, and X a in the anhydride are the same as Z in the as-synthesized polyetherimide; or
the anhydride is of the formula
wherein R a and R b are each independently the same or different, and are a halogen atom or a monovalent C 1-6 alkyl group; p and q are each independently integers of 0 to 4; c is 0 to 4; X a is a C 1-18 bridging group; and R a , R b , p, q, and X a in the anhydride are the same as Z in the as-synthesized polyetherimide; or
the anhydride is of the formula
when Z is derived from bisphenol A in the as-synthesized polyetherimide.
11. The method of claim 1 , comprising the anhydride, wherein the anhydride is of the formula
wherein Z and R are the same as in the as-synthesized polyetherimide, and X is a hydrogen atom, halogen atom, or a nitro group.
12. The method of claim 1 , comprising the anhydride, wherein R in the as-synthesized polyetherimide is derived from meta-phenylene, and
the anhydride is of the formula
wherein R a and R b are each independently the same or different, and are a halogen atom or a monovalent C 1-6 alkyl group; p and q are each independently integers of 0 to 4; c is 0 to 4; X a is a C 1-18 bridging group; and X is a hydrogen atom, halogen atom, or a nitro; and R a , R b , p, q, c, and X a are the same as Z in the as-synthesized polyetherimide; or
the anhydride is of the formula
wherein R a and R b are each independently the same or different, and are a halogen atom or a monovalent C 1-6 alkyl group; p and q are each independently integers of 0 to 4; c is 0 to 4; X a is a C 1-18 bridging group; and X is a hydrogen atom, halogen atom, or a nitro; and R a , R b , p, q, and X a are the same as Z in the as-synthesized polyetherimide; or
the anhydride is of the formula
wherein Z is derived from bisphenol A in the as-synthesized polyetherimide, and X is a hydrogen atom, halogen atom, or a nitro group.
13. The method of claim 1 , wherein the isolated polyetherimide composition comprises a dianhydride of the formula
in an amount of 0 to 3,000 parts per million.
14. The method of claim 1 , wherein the isolated polyetherimide composition further comprises up to 5,000 parts per million of a bis(phthalimide) of the formula
15. The method of claim 1 , wherein the isolated polyetherimide composition has
a Yellowness Index of less than 150, as determined in accordance with ASTM D1925-00 on a molded sample having a thickness of 3.2 millimeters.
16. The method of claim 1 , wherein the melt extruding is at 150 to 420° C.
17. An isolated polyetherimide composition made by the method of claim 1 , comprising
a polyetherimide comprising units of the formula
and
(a) a tri(C 8-30 acyl) glyceride, an anhydride of the formula
or a combination thereof, or
(b) a residual component from the manufacture of the as-synthesized polyetherimide, or
(c) a combination comprising (a) and (b);
wherein, in the foregoing formulas,
each R is independently a substituted or unsubstituted C 6-30 aromatic hydrocarbon group, a substituted or unsubstituted, straight or branched chain C 4-30 alkylene group, a substituted or unsubstituted C 3-8 cycloalkylene group, or a combination thereof;
each Z is independently an aromatic C 6-30 monocyclic or polycyclic group optionally substituted with 1 to 6 C 1-8 alkyl groups, 1 to 8 halogen atoms, or a combination thereof, and
G is a hydrogen atom, a halogen atom, a nitro group, C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl, C 1-12 haloalkyl, C 1-12 alkoxy, C 1-12 haloalkoxy, C 3-12 cycloalkyl, C 5-12 cycloalkenyl, C 6-18 aryl, C 7-31 arylalkylene, C 7-31 alkylarylene, C 4-12 heterocycloalkyl, C 3-18 heteroaryl, C 1-12 alkyl sulfonyl, C 6-12 arylsulfonyl, tosyl, or a group of the formulas
wherein
T is —O—Z—O—, a single bond, —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R a )(═O)—wherein R a is C 1-8 alkyl or C 6-12 aryl, NR b wherein R b is a hydrogen atom, C 1-8 alkyl, or C 6-12 aryl, or T is a C 1-18 organic bridging group, and
X is chloro, bromo, iodo, or nitro, or a combination thereof.
18. The isolated polyetherimide composition of claim 17 , wherein the groups R and Z in the polyetherimide are not the same as any groups R and Z in the anhydride.
19. An article comprising the isolated polyetherimide composition made by the method of claim 1 .
20. The isolated polyetherimide composition of claim 17 , wherein the change in complex viscosity is from 0 to −20%, measured over 30 minutes at 390° C., at a shear rate of 6.28 rad/seconds, strain=5%, and under nitrogen.