Polyetherimides, methods of manufacture, and articles formed therefrom

Patent metadata

Field	Value
Publication number	US-9127128-B2
Application number	US-201113283965-A
Country	US
Kind code	B2
Filing date	Oct 28, 2011
Priority date	Oct 28, 2011
Publication date	Sep 8, 2015
Grant date	Sep 8, 2015

Abstract

A polyetherimide composition comprising a polyetherimide manufactured by reaction of an alkali metal salt of a dihydroxy aromatic compound with a bis(halophthalimide) composition comprising, based on the weight of the bis(halophthalimide) composition,
at least 15 wt. % of a 3,3′-bis(halophthalimide) of the formula

from more than 17 wt. % to less than 85 wt. % of a 4,3′-bis(halophthalimide) of the formula

from more than 0 to less than 27 wt. % of a 4,4′-bis(halophthalimide) of the formula

First claim

What is claimed is:

1. A polymer composition comprising a polyetherimide having the formula

wherein
n is greater than 1,
each R is the same or different, and is selected from an aromatic hydrocarbon group having 6 to 30 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a divalent group of the formula

wherein Q 1 is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, and —C y H 2y —wherein y is 1 to 5 and a halogenated derivative thereof,
each Z is the same or different, and is an aromatic C 6-24 monocyclic or polycylic polycyclic moiety optionally substituted with 1 to 6 C 1-18 alkyl groups, 1 to 8 halogen atoms, or a combination thereof , and
the divalent bonds between the —O—Z—O—group and the phenyl substituents are in the 3,3′, 3,4′, 4,3′, and 4,4′ positions, the divalent bonds of the —O—Z—O—group being made from a bis(halophthalimide) composition comprising, based on the weight of the bis(halophthalimide) composition,
at least 15 wt.% of a 3,3′-bis(halophthalimide) of the formula

from more than 17 wt.% to less than 85 wt.% of a 4,3′-bis(halophthalimide) of the formula

from more than 0 to less than 27 wt.% of a 4,4′-bis(halophthalimide) of the formula

wherein each X is independently fluoro, chloro, bromo, or iodo and R is as defined above,
wherein the composition comprises less than 1.5 wt% of a monocyclic adduct of the bis(halophthalimide) composition and an alkali metal salt of a dihydroxy aromatic compound of the formula
MO—Z—OM

wherein M is an alkali metal and Z in the dihydroxy aromatic compound is the same as the Z in polyetherimide; and
wherein the polyetherimide has a glass transition temperature of greater than 180° C.

2. A polyetherimide composition manufactured by reaction of an alkali metal salt of a dihydroxy aromatic compound of the formula
MO—Z—OM

wherein M is an alkali metal and 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 thereof, with
a bis(halophthalimide) composition comprising, based on the weight of the bis(halophthalimide) composition,
at least 15 wt.% of a 3,3′-bis(halophthalimide) of the formula

from more than 17 wt.% to less than 85 wt.% of a 4,3′-bis(halophthalimide) of the formula

from more than 0 to less than 27 wt.% of a 4,4′-bis(halophthalimide) of the formula

wherein
each R is selected from an aromatic hydrocarbon group having 6 to 30 carbon atoms, a halogenated derivative thereof, a straight or branched chain alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a divalent group of the formula

wherein Q′ is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, and —C y H 2y —wherein y is 1to 5 and a halogenated derivative thereof, and
each X is independently fluoro, chloro, bromo, or iodo, and further wherein
the polyetherimide is of the formula

wherein n is greater than 1, each R is the same or different, each Z is the same or different, and are as defined above, and the divalent bonds between the —O—Z—O—group and the phenyl substituents are in the 3,3′, 3,4′, 4,3′, and 4,4′ positions,
wherein the composition comprises less than 1.5 wt% of a monocyclic adduct of the bis(halophthalimide) composition and the alkali metal salt of the formula
MO—Z—OM.

3. The composition of claim 1 , wherein the polyetherimide has
a heat deflection temperature of at least 218° C., determined in accordance with ASTM 648 on a molded sample,
a heat deflection temperature at least 10° C. higher than a heat deflection temperature of the same polyetherimide manufactured using a bis(halophthalimide) composition comprising more than 10 wt.% of the 4,3′-bis(halophthalimide), each determined in accordance with ASTM 648 at 0.455 megaPascals stress and at 3.2 millimeters thickness on a molded sample,
at least 10% higher stiffness than a stiffness of the same polyetherimide manufactured using the bis(halophthalimide) composition comprising more than 10 wt.% of the 4,3′-bis(halophthalimide), each determined by dynamic mechanical analysis over 30° C. to 210° C. on a molded sample, and
a ratio of a high shear rate viscosity to a low shear rate viscosity that is at least 30% higher than the same ratio of the same polyetherimide manufactured using the bis(halophthalimide) composition comprising more than 10wt.% of the 4,3′-bis(halophthalimide), each determined by parallel plate rheometry.

4. The composition of claim 1 , wherein
the bis(halophthalimide) composition comprises from more than 47 wt.% to less than 85 wt.% of the 4,3′-bis(halophthalimide).

5. The composition of claim 4 , wherein the polyetherimide comprises, based on parts of the polyetherimide,
less than 100 parts per million each of the 3,3′-bis(halophthalimide), the 4,3′-bis(halophthalimide), and the 4,4′-bis(halophthalimide).,
less than 100 parts per million of a halo(bisphthalimide) of the formula

less than 100 parts per million of a bisphthalimide of the formula

less than 200 parts per million of a total of the 3,3′-bis(halophthalimide), the 4,3 ′-bis(halophthalimide), the 4,4′-bis(halophthalimide), and the halo(bisphthalimide).

6. The composition of claim 4 , wherein
the polyetherimide has a heat deflection temperature of at least 218° C., determined in accordance with ASTM 648 on a molded sample,
the polyetherimide has a heat deflection temperature at least 10° C. higher than the heat deflection temperature of the same polyetherimide manufactured using the bis(halophthalimide) composition comprising less than 10 wt.% of the 4,3′-bis(halophthalimide) and more than 27wt.% of the 4,4′-bis(halophthalimide), each determined in accordance with ASTM 648 at 0.455 megaPascals stress and at 3.2 millimeters thickness on a molded sample,
the polyetherimide has at least 10% higher stiffness than the stiffness of the same polyetherimide manufactured using the bis(chlorophthalimide) composition comprising less than 10 wt.% of the 4,3′-bis(halophthalimide) and more than 27 wt.% of the 4,4′-bis(halophthalimide), each determined by dynamic mechanical analysis over 30° C. to 210° C., on a molded sample, and
the polyetherimide has a ratio of a high shear rate viscosity to a low she

Assignees

• Kuhlman Matthew L
• Haralur Gurulingamurthy M
• Sabic Global Technologies Bv

Inventors

• Kuhlman Matthew L
• Haralur Gurulingamurthy M

Classifications

• C08G73/1046

  Polyimides containing oxygen in the form of ether bonds in the main chain · CPC title

• C08L79/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• Y10T428/298

  Physical dimension · CPC title

• C08G73/1053 Primary

  with oxygen only in the tetracarboxylic moiety · CPC title

• C08G73/1042 Primary

  Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds · CPC title