Compositions and articles made from branched polyetherimides

1. A branched polyimide of the formula

wherein, in the formula,

G is a group having a valence of t, present in an amount of 0.01 to 10 mol %,

each Q is independently the same or different, and is a divalent C 1-60 hydrocarbon group,

each M is independently the same or different, and is —O—, —C(O)—, —OC(O)—, —OC(O)O—, —NHC(O), —(O)CNH—, —S—, —S(O)—, or —S(O) 2 —,

D is a phenylene,

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,

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

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

wherein the branched polyimide has

a zero-shear viscosity in a range from 500 to 15,000 Pascal·seconds, measured at 360° C.,

a rheology ratio of 1.1 to 5, wherein the rheology ratio is the ratio of viscosity at a shear rate of 10/s to viscosity at a shear rate of 100/s, measured at 360° C., and

a strain hardening ratio of 1 to 6, wherein the strain hardening ratio is the ratio of extensional viscosity at a Hencky strain of 3 to extensional viscosity at a Hencky strain of 0.5, measured at 300° C. and a strain rate of 2/s.

2. The branched polyimide of claim 1 , wherein the branched polyimide has

a weight average molecular weight of 30,000 to 40,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, wherein

G is present in an amount of 0.3 to 0.5 mole percent, the rheology ratio is 1.1 to 1.5, and the strain hardening ratio is 1.1 to 1.5; or

G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 1.3 to 1.7, and the strain hardening ratio is 1.5 to 2.5; or

G is present in an amount of 2 to 3 mole percent, the rheology ratio is 1.6 to 2, and the strain hardening ratio is 2.5 to 3.

3. The branched polyimide of claim 1 , wherein the branched polyimide has

a weight average molecular weight of 40,100 to 52,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, wherein

G is present in an amount of 0.3 to 0.5 mole percent, the rheology ratio is 1.5 to 2.5, and the strain hardening ratio is 3 to 4; or

G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 2 to 2.5, and the strain hardening ratio is 4 to 5; or

G is present in an amount of 2 to 3 mole percent, the rheology ratio is 2.5 to 3, and the strain hardening ratio is 4.5 to 5.

4. The branched polyimide of claim 1 , wherein the branched polyimide has

a weight average molecular weight of 52,100 to 68,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, wherein

G is present in an amount of 0.3 to 0.5 mole percent, the rheology ratio is 2 to 4, and the strain hardening ratio is 3 to 6; or

G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 2.5 to 4, and the strain hardening ratio is 4 to 6; or

G is present in an amount of 2 to 3 mole percent, the rheology ratio is 3 to 4, and the strain hardening ratio is 5 to 6.

5. The branched polyimide of claim 1 , wherein the branched polyimide has at least one of:

a melt flow rate of 2 to 25 grams per 10 minutes, measured at 337° C. according to ASTM D1238-10; or

a glass transition temperature of greater than 100° C., as determined by differential scanning calorimetry; or

a viscosity increase of 25 to 1,000%, measured at 400° C. and a shear rate of 640/s; or

an apparent viscosity of 350 to 1,200 Pascal·seconds, at a shear rate of 640/s; or

a tensile elongation at break of greater than 8%, measured at 23° C. according to ASTM D638; or

a notched Izod impact strength of at least 25 Joules per meter, measured at 23° C. according to ASTM D256-10; or

an unnotched Izod impact strength of at least 1,000 Joules per meter, measured at 23° C. according to ASTM D256-10; or

a reverse notched Izod impact strength of at least 600 Joules per meter, measured at 23° C. according to ASTM D256-10.

6. The branched polyimide of claim 1 , wherein V is a group of the formula

wherein W is —O—, —S—, —C(O)—, —SO 2 —, —SO—, —P(R a )(═O)—wherein R a 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.

7. The branched polyimide of claim 1 , wherein the branched polyimide is a branched polyetherimide of the formula

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.

8. The branched polyimide of claim 7 , wherein Z is a divalent group of the formula

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; and

R is m-phenylene, p-phenylene, bis(4,4′-phenylene)sulfone, bis(3,4′-phenylene)sulfone, or bis(3,3′-phenylene)sulfone.

9. A method for the manufacture of the branched polyimide of claim 1 , the method comprising reacting

a polyamine of the formula

and a diamine of the formula

H 2 N—R—NH 2

with either

a dianhydride of the formula

an anhydride of the formula

in a solvent and under conditions effective to provide the branched polyimide, wherein G, Q, M, D, R, V, q, m, d, p, and t are as defined in claim 1 , and wherein X is a nitro group or halogen.

10. The method of claim 9 , further comprising

pre-dissolving the polyamine and the diamine in a first portion of the solvent to form a first mixture;

pre-dissolving the dianhydride in a second portion of the solvent to form a second mixture; and

combining the first mixture and the second mixture.

11. The method of claim 9 , wherein the branched polyimide is a branched polyetherimide, and the method comprises:

reacting

the polyamine of the formula

and the diamine of the formula

H 2 N—R—NH 2

with the anhydride of the formula

wherein X is a nitro group or halogen, to provide intermediate bis(phthalimide)s of the formulas

reacting the bis(phthalimide)s with an alkali metal salt of a dihydroxy aromatic compound having the formula

AMO—Z—OAM

wherein AM is an alkali metal, to provide the branched polyetherimide, wherein G, Q, M, D, R, V, Z, q, m, d, p, and t are as defined in claim 1 .

12. The method of claim 9 , wherein the polyamine is of the formula

13. An article comprising a polymer composition, wherein the polymer composition comprises the branched polyimide of claim 1 ; and a second polymer different from the branched polyimide.

14. The article of claim 13 , wherein the second polymer is a polyacetal, poly(C 1-6 alkyl)acrylate, polyacrylamide, polyacrylonitrile, polyamide, polyamideimide, polyanhydride, polyarylene ether, polyarylene ether ketone, polyarylene ketone, polyarylene sulfide, polyarylene sulfone, polybenzothiazole, polybenzoxazole, polybenzimidazole, polycarbonate, polyester, polyetherimide, polyimide, poly(C 1-6 alkyl)methacrylate, polymethacrylamide, cyclic olefin polymer, polyolefin, polyoxadiazole, polyoxymethylene, polyphthalide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine, polyurea, polyurethane, vinyl polymer, or a combination thereof.

15. The article of claim 13 , wherein the article is a thin-walled component,

wherein the branched polyimide has

a weight average molecular weight of 30,000 to 40,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.3 to 0.5 mole percent, the rheology ratio is 1.1 to 1.5, and the strain hardening ratio is 1.1 to 1.5; or

a weight average molecular weight of 40,100 to 52,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 2 to 3 mole percent, the rheology ratio is 2.5 to 3, and the strain hardening ratio is 4.5 to 5; or

a weight average molecular weight of 52,100 to 68,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 2 to 3 mole percent, the rheology ratio is 3 to 4, and the strain hardening ratio is 5 to 6.

16. The article of claim 13 , wherein the article is a thermoformed article,

wherein the branched polyimide has

a weight average molecular weight of 30,000 to 40,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 1.3 to 1.7, and the strain hardening ratio is 1.5 to 2.5; or

a weight average molecular weight of 52,100 to 68,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 2.5 to 4, and the strain hardening ratio is 4 to 6; or

a weight average molecular weight of 40,100 to 52,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.3 to 0.5 mole percent, the rheology ratio is 1.5 to 2.5, and the strain hardening ratio is 3 to 4.

17. The article of claim 13 , wherein the article is a spun fiber, wherein the branched polyimide has

a weight average molecular weight of 30,000 to 40,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 2 to 3 mole percent, the rheology ratio is 1.6 to 2, and the strain hardening ratio is 2.5 to 3; or

a weight average molecular weight of 52,100 to 68,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 2 to 3 mole percent, the rheology ratio is 3 to 4, and the strain hardening ratio is 5 to 6; or

a weight average molecular weight of 40,100 to 52,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 2 to 2.5, and the strain hardening ratio is 4 to 5.

18. The article of claim 13 , wherein the article is a foam, wherein the branched polyimide has

a weight average molecular weight of 30,000 to 40,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 2 to 3 mole percent, the rheology ratio is 1.6 to 2, and the strain hardening ratio is 2.5 to 3; or

a weight average molecular weight of 40,100 to 52,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 2 to 2.5, and the strain hardening ratio is 4 to 5; or

a weight average molecular weight of 52,100 to 68,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 2.5 to 4, and the strain hardening ratio is 4 to 6.

19. The article of claim 13 , wherein the article is a foam, wherein the branched polyimide has

a weight average molecular weight of 30,000 to 40,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 2 to 3 mole percent, the rheology ratio is 1.6 to 2, and the strain hardening ratio is 2.5 to 3; or

a weight average molecular weight of 40,100 to 52,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 2 to 2.5, and the strain hardening ratio is 4 to 5; or

a weight average molecular weight of 52,100 to 68,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 2.5 to 4, and the strain hardening ratio is 4 to 6.

20. The article of claim 13 , wherein the article is an additive for large format manufacturing, wherein the branched polyimide has

a weight average molecular weight of 30,000 to 40,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.5 to 2 mole percent, the rheology ratio is 1.3 to 1.7, and the strain hardening ratio is 1.5 to 2.5; or

a weight average molecular weight of 40,100 to 52,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.3 to 0.5 mole percent, the rheology ratio is 1.5 to 2.5, and the strain hardening ratio is 3 to 4; or

a weight average molecular weight of 52,100 to 68,000 grams per mole, as measured by gel permeation chromatography using a triple point detector, G is present in an amount of 0.3 to 0.5 mole percent, the rheology ratio is 2 to 4, and the strain hardening ratio is 3 to 6.