Compositions and articles made from branched polyetherimides

Patent metadata

Field	Value
Publication number	US-11286347-B2
Application number	US-201716472150-A
Country	US
Kind code	B2
Filing date	Dec 29, 2017
Priority date	Dec 31, 2016
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

Abstract

A branched polyimide of the formula (I) wherein G is a group having a valence of t, present in an amount of 0.01 to 10 mol %, or 0.05 to 5 mol %, or 0.1 to 4 mol %, or 0.1 to 3 mol %, each of Q, M, D, V, and R are as defined herein, 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, preferably 2 to 4, 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, wherein the branched polyimide has a zero-shear viscosity in a range from 500 to 15,000 Pa·s, a rheology ratio of 1.1 to 5, and a strain hardening ratio of 1 to 6.

First claim

The invention claimed is:

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

Assignees

• Sabic Global Technologies Bv
• Shpp Global Tech Bv

Inventors

• Odle Roy Ray
• Johnson Peter
• Chellamuthu Manojkumar
• Kong Hee Won

Classifications

• C08G73/122

  containing chain terminating or branching agents · CPC title

• C08L79/08

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

• C08G73/1007

  from tetracarboxylic acids or derivatives and diamines · CPC title

• C08J2205/052

  Closed cells, i.e. more than 50% of the pores are closed · CPC title

• C08L2203/14

  used for foams · CPC title