Polyetherimide from metal free ionomers

1. A polyimide oligomer of formula (1a), (1b), a copolymer thereof, or a combination thereof,

wherein

each G 1 is independently the same or different, and is a cation group;

each G 2 is independently the same or different, and is an anion group;

each D is independently the same or different, and is a single bond or C 1-20 divalent hydrocarbon group;

each V is independently the same or different, and is a tetravalent C 4-40 hydrocarbon group;

each R is independently the same or different, and is a C 1-20 divalent hydrocarbon group;

each n is independently the same or different, and is 1 to 1,000, provided that the total of all values of n is greater than 4; and

t is 2 to 1000.

2. The polyimide oligomer of claim 1 , wherein

each G 1 is independently ammonium, phosphonium, sulfonium, imidazolium, guanidinium, or pyridinium; and

each G 2 is independently carboxylate, sulfate, sulfonate, phosphate, phosphinate, or phosphonate.

3. The polyimide oligomer of claim 1 , wherein

each D is independently substituted or unsubstituted C 1-20 alkylene, substituted or unsubstituted C 3-8 cycloalkylene, substituted or unsubstituted C 6-20 arylene, or substituted or unsubstituted C 3-12 heteroarylene;

G 1 is —N(R a )(R b )(R c )— or —P(R a )(R b )(R c )—; and

G 2 is —C(O)O—, —S(O) 2 O—, —OP(O)(OR d )O—, —P(O)(R e )O—, —P(O)(OR f )O—, or —OP(O)(R g )O— wherein R a , R b , R c , R d , R e , R f , and R g are each independently hydrogen, substituted or unsubstituted C 1-8 alkyl, or substituted or unsubstituted C 6-12 aryl.

4. The polyimide oligomer of claim 1 , wherein V is a group of the formulas

wherein W is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R h )(═O)— wherein R h 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 a group of the formula —O—Z—O— wherein 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, provided that the valence of Z is not exceeded.

5. The polyimide oligomer of claim 1 , wherein structural units of formula (2)

are divalent groups of formula (2a)

wherein each Z is independently 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, provided that the valence of Z is not exceeded.

6. The polyimide oligomer of claim 5 , wherein Z is a divalent group of formula (3a)

wherein J is —O—, —S—, —C(O)—, —SO 2 —, —SO—, or —C y H 2y — wherein y is an integer from 1 to 5 or a halogenated derivative thereof.

7. The polyimide oligomer of claim 6 , wherein J is isopropylidene and R is m-phenylene.

8. The polyimide oligomer of claim 1 , wherein G 1 is —P(Ph) 3 -, G 2 is —S(O) 2 O—, and D is meta-phenylene.

9. The polyimide oligomer of claim 1 , having one or more of the following properties:

a T g of greater than 160° C., as determined by differential scanning calorimetry; or

a thermal decomposition temperature of greater than 450° C., as determined at a 5% weight loss by thermogravimetric analysis; or

a tensile yield strength of greater than 70 megapascals, as determined by ASTM D638; or

a tensile break strength of greater than 70 megapascals, as determined by ASTM D638.

10. A method for the manufacture of the polyimide oligomer of claim 1 , the method comprising:

reacting

a diamine of formula (4)

H 2 N—R—NH 2   (4)

with a dianhydride of formula (5)

in a solvent and under conditions effective to provide an anhydride-capped oligomer; and

reacting the anhydride-capped oligomer with amino compounds of formulas (6a) and (6b)

H 2 N-D-G 1 -A  (6a)

H 2 N-D-G 2 -M′  (6b)

under conditions effective to provide the polyimide oligomer of formula (1a) or under conditions effective to provide the polyimide oligomer of formula (1b), wherein

A is an anion,

M′ is a cation, and

R, V, D, G, and G 2 are as defined in claim 1 .

11. The method of claim 10 , wherein

A is Cl − , Br − , I − , a substituted or unsubstituted (C 1-24 hydrocarbyl)carboxylate, HCO 3 − , CO 3 2− , CH 3 SO 4 − , HSO 4 − , SO 4 2− , H 2 PO 4 − , HPO 4 2− , PO 4 3− , NO 3 − , p-toluenesulfonate, bis(trifluoromethanesulfonyl)imide, or a combination thereof; and

M′ is Li + , Na + , K + , Mg 2+ , Ca 2+ , Sr 2+ , Zn 2+ , ammonium, phosphonium, imidazolium, guanidinium, pyridinium, or a combination thereof.

12. The method of claim 10 , wherein 0.1 to 20 mole percent of the diamine (4) is replaced by a branching polyamine of formula (4a)

wherein

G is a group having a valence of t,

each Q is independently the same or different, and is a substituted or unsubstituted divalent C 1-60 hydrocarbon group, —O—, —C(O)O—, —OC(O)O—, —S—, —S(O 3 )—, —OS(O) 3 —, or —OP(O) 3 —,

each M is independently the same or different, and is a substituted or unsubstituted divalent C 1-60 hydrocarbon group, —O—, —C(O)—, —OC(O)—, —OC(O)O—, —NHC(O), —(O)CNH—, —S—, —S(O)—, or —S(O) 2 —,

each D is independently the same or different, and is a single bond or C 1-20 divalent hydrocarbon group,

q is 0 or 1, m is 0 or 1, d is 0 or 1, p is 1 or 2, and t is 3 to 6.

13. The method of claim 10 , wherein the conditions effective to provide the polyimide oligomer of formula (1a) and/or of formula (1b) comprise adding an organic solvent, water, or a combination thereof, to provide the polyimide oligomer of formula (1a) and/or of formula (1b).

14. A polymer composition comprising:

the polyimide oligomer of claim 1 ; and

a second polymer that is different from the polyimide oligomer.

15. An article comprising the polyimide oligomer of claim 1 .

16. The article of claim 15 , wherein the article is a film, a foam, a membrane, a conducting part, a fiber, a lens, a varnish, or a composite.

17. The article of claim 15 , wherein the article is an open cell foam, a closed cell foam, a nano-foam, a battery separator, an ion exchange membrane, tubing, a capillary, a coating, or a scratch resistant part.