Polyimide and polyetherimide from metal containing oligomers

• US 10,619,010 B2
• Filed: 12/31/2018
• Issued: 04/14/2020
• Est. Priority Date: 12/31/2016
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Odle, Roy Ray, Cao, Ke, Liu, Guoliang, Long, Timothy Edward, Dennis, Joseph Michael
• Primary Examiner(s): Fang, Shane
• Application Number:
  US16/236,717
• Publication Number:
  US 20190211153A1
• Time in Patent Office: 470 Days
• CPC Class Codes: C08G 73/1007 from tetracarboxylic acids or derivatives and diamines
• CPC Class Codes: C08G 73/101 containing chain terminating or branching agents
• CPC Class Codes: C08G 73/1046 Polyimides containing oxygen in the form of ether bonds in the main chain
• CPC Class Codes: C08G 73/1071 Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• CPC Class Codes: C08G 73/122 containing chain terminating or branching agents
• CPC Class Codes: C08L 2203/12 used for fibers
• CPC Class Codes: C08L 2203/14 used for foams
• CPC Class Codes: C08L 2205/025 containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• CPC Class Codes: C08L 2205/03 containing three or more polymers in a blend
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Abstract

A polyimide oligomer of the formula

wherein G is a group having a valence of t, each R is independently a C_1-30 divalent bridging group, a C_1-20 alkylene-X, or a C_6-30 arylene-X wherein —X is —O-M′, —C(O)O-M′, —OC(O)O-M′, —S-M′, —S(O)₂-M′, —S(O)₃-M′, —OS(O)₃-M′, or —OP(O)₃-M′ wherein each M′ is independently Li, Na, K, Cs, Mg, Ca, Sr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, B, Al, Ga, In, Ge, Sn, Pb, As, or Sb, provided that at least one R is C_1-20 alkylene-X or C_6-30 arylene-X, q is 0 or 1, m is 0 or 1, d is 0 or 1, p is 1 or 2, t is 1 to 6, and each n is independently 1 to 1,000, the total of all values of n is greater than 4, the polyimide oligomer is thermoplastic, and Q, M, D, and V are as provided herein.

Claims

1. A polyimide oligomer of the formula

2. The polyimide oligomer of claim 1, wherein

t is 1, G is Li, Na, K, Mg, Ca, Sr, or Zn, Q is —

O—

, —

C(O)O—

, —

OC(O)O—

, —

S—

, —

S(O₃)—

, —

OS(O)₃—

, or —

OP(O)₃—

, and at least one R is a C_1-20 alkylene-X or a C_6-30 arylene-X wherein —

X is —

O-M′

, —

C(O)O-M′

, —

OC(O)O-M′

, —

S-M′

, —

S(O)₂-M′

, —

S(O)₃-M′

, —

OS(O)₃-M′

, or —

OP(O)₃-M′

, and wherein each M′

is independently Li, Na, K, Mg, Ca, Sr, or Zn;

or

t is 2, G is Mg, Ca, Sr, or Zn, Q is —

O—

, —

C(O)O—

, —

OC(O)O—

, —

S—

, —

S(O₃)—

, —

OS(O)₃—

, or —

OP(O)₃—

, and at least one R is a C_1-20 alkylene-X or a C_6-30 arylene-X wherein —

X is —

O-M′

, —

C(O)O-M′

, —

OC(O)O-M′

, —

S-M′

, —

S(O)₂-M′

, —

S(O)₃-M′

, —

OS(O)₃-M′

, or —

OP(O)₃-M′

, and wherein M′

is Li, Na, K, Mg, Ca, Sr, or Zn;

or

t is 2, G is —

O—

, —

C(O)—

, —

OC(O)—

, —

(O)CO—

, —

NHC(O), —

(O)CNH—

, —

S—

, —

S(O)—

, —

S(O)₂—

, or —

P(R^a)(O)—

wherein R^a is a C_1-8 alkyl or C_6-12 aryl, and at least one R is a C_1-20 alkylene-X or a C_6-30 arylene-X wherein —

X is —

O-M′

, —

C(O)O-M′

, —

OC(O)O-M′

, —

S-M′

, —

S(O)₂-M′

, —

S(O)₃-M′

, —

OS(O)₃-M′

, or —

OP(O)₃-M′

, and wherein M′

is Li, Na, K, Mg, Ca, Sr, or Zn;

or

t is greater than 2, G is Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, B, Al, Ga, In, Sn, Pb, As, Sb, Ti, Zr, Ge, Sn, or a substituted or unsubstituted C_1-60 hydrocarbon group having a valence of t, G is present in an amount of 0.01 to 20 mol %, and at least one R is a C_1-20 alkylene-X or a C_6-30 arylene-X wherein —

X is —

O-M′

, —

C(O)O-M′

, —

OC(O)O-M′

, —

S-M′

, —

S(O)₂-M′

, —

S(O)₃-M′

, —

OS(O)₃-M′

, or —

OP(O)₃-M′

, and wherein each M′

is independently Li, Na, K, Mg, Ca, Sr, or Zn.

3. The polyimide oligomer of claim 1, wherein the C_1-30 divalent bridging group of R is the same or different C_6-20 organic bridging group or a halogenated derivative thereof, a straight or branched chain C_2-20 alkylene group or a halogenated derivative thereof, or a C_3-8 cycloalkylene group or halogenated derivative thereof.

4. The polyimide oligomer of claim 1, wherein m is 0, t is 2, Q is —

C(O)O—

or —

S(O₃)—

, and G is Mg, Ca, Sr, or Zn.

5. The polyimide oligomer of claim 1, wherein m is 0, t is 2, Q is —

C(O)O—

or —

S(O₃)—

, G is Mg, Ca, Sr, or Zn, and at least one R is a C_1-20 alkylene-X or a C_6-30 arylene-X wherein —

X is —

C(O)O-M′

or —

S(O)₃-M′

, and wherein each M′

is independently Li, Na, K, Mg, Ca, Sr, or Zn.

6. The polyimide oligomer of claim 1, wherein m is 0, t is 1, Q is —

C(O)O—

or —

S(O₃)—

, and at least one R is a C_1-20 alkylene-X or a C_6-30 arylene-X wherein —

X is —

C(O)O-M′

or —

S(O)₃-M′

, and wherein each M′

is independently Li, Na, K, Mg, Ca, Sr, or Zn.

7. The polyimide oligomer of claim 1, wherein G is —

O—

, a substituted or unsubstituted C_1-20 alkylene, a substituted or unsubstituted C_3-8 cycloalkylene, a substituted or unsubstituted C_6-20 arylene, or a substituted or unsubstituted C_3-12 heteroarylene.

8. The polyimide oligomer of claim 1, wherein q is 1, Q is a C_6-20 arylene, m is 1, and M is —

O—

.

9. The polyimide oligomer of claim 1, wherein V is a group of the formula

10. The polyimide oligomer of claim 1, wherein the polyimide oligomer is a polyetherimide oligomer of the formula

11. The polyimide oligomer of claim 10, wherein Z is a divalent group of the formula

12. The polyimide oligomer of claim 11, wherein J is isopropylidene, at least one R is m-phenylene, and at least one R is phenylene-X wherein —

X is —

S(O)₃-M′ and

each M is independently Li, Na, K, Mg, Ca, Sr, or Zn.

13. The polyimide oligomer of claim 1, having one or more of:

a T_g greater than 160°

C., or

a thermal decomposition temperature of greater than 450°

C., as determined at a 5% weight loss by thermogravimetric analysis;

or

a polydispersity of 1.5 to 3, as determined by size exclusion chromatography multi-angle light scattering.

14. A method for the manufacture of the polyimide oligomer of claim 1, the method comprising reacting

a diamine of the formula

H₂N—

R¹—

NH₂

with a dianhydride of the formula

15. A method for the manufacture of the polyimide oligomer of claim 1, wherein the polyimide oligomer is a polyetherimide oligomer, the method comprising:

reacting

a diamine of the formula

H₂N—

R¹—

NH₂

with an anhydride of the formula

16. A polymer composition comprising:

the polyimide oligomer of claim 1; and

a second polymer different from the polyimide oligomer.

17. The polymer composition of claim 16, 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.

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

19. The article of claim 18, wherein the article is a film, a foam, a membrane, a conducting part, a fiber, a lens, a varnish, or a composite.

20. A method for manufacturing the article of claim 18, wherein the method comprises melt processing, solvent casting, additive manufacturing, or a combination thereof.