Polyetherimides, methods of manufacture, and articles formed therefrom

• US 9,315,702 B2
• Filed: 07/31/2015
• Issued: 04/19/2016
• Est. Priority Date: 10/28/2011
• Status: Active Grant

• Current Assignee: SHPP Global Technologies BV
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Kuhlman, Matthew L., Haralur, Gurulingamurthy M.
• Primary Examiner(s): Listvoyb, Gregory
• Application Number:
  US14/814,701
• Publication Number:
  US 20150337187A1
• Time in Patent Office: 263 Days
• US Class Current: 1/1
• CPC Class Codes: C08G 73/1003 Preparatory processes
• CPC Class Codes: C08G 73/1042 Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• CPC Class Codes: C08G 73/1046 Polyimides containing oxygen in the form of ether bonds in the main chain
• CPC Class Codes: C08G 73/1053 with oxygen only in the tetracarboxylic moiety
• CPC Class Codes: C08G 79/08 a linkage containing boron
• CPC Class Codes: C08J 2379/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08J 5/00 Manufacture of articles or shaped materials containing macromolecular substances manufacture of semi-permeable membranes B01D67/00 - B01D71/00
• CPC Class Codes: C08K 3/01 characterized by their specific function
• CPC Class Codes: C08K 5/0008 Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C09D 179/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C09J 179/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: Y10T 428/298 Physical dimension
• CPC Class Codes: Y10T 428/31681 Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

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

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

Claims

1. A polymer composition comprising a polyetherimide having the formula

3. The composition of claim 1, wherein

the bis(chlorophthalimide) composition comprises greater than 17 wt. % of the 4,3′

-bis(chlorophthalimide) and less than 15 wt. % of the 4,4′

-bis(chlorophthalimide), and

the polyetherimide has a heat deflection temperature at least 10°

C. higher than a heat deflection temperature of the same polyetherimide manufactured using a bis(chlorophthalimide) composition comprising less than 10 wt. % of the 4,3′

-bis(chlorophthalimide) and more than 15 wt. % of the 4,4′

-bis(chlorophthalimide), each determined in accordance with ASTM 648 at 0.455 megaPascals stress and at 3.2 millimeters thickness on a molded sample.

4. The composition of claim 1, wherein

the bis(chlorophthalimide) composition comprises greater than 17 wt. % of the 4,3′

-bis(chlorophthalimide), and less than 15 wt. % of 4,4′

-bis(chlorophthalimide), and

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(chlorophthalimide), and more than 15 wt. % of the 4,4′

-bis(chlorophthalimide), each determined by dynamic mechanical analysis over 30°

C. to 210°

C., on a molded sample.

5. The composition of claim 1, wherein

the bis(chlorophthalimide) composition comprises greater than 17 wt. % of a 4,3′

-bis(chlorophthalimide), and less than 15 wt. % of 4,4′

-bis(chlorophthalimide), and

the polyetherimide has 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 a bis(chlorophthalimide) composition comprising less than 10 wt. % of one or both of the 4,3′

-bis(chlorophthalimide) and more than 15 wt. % of the 4,4′

-bis(chlorophthalimide), each determined by parallel plate rheometry.

6. The composition of claim 1, wherein

R is a divalent radical of the formula

7. The composition of claim 6, wherein Z is 2,2-(4-phenylene)isopropylidene and R is m-phenylene, p-phenylene diarylsulfone, or a combination thereof.

8. The composition of claim 1, wherein the bis(halophthalimide) composition comprises

from 15 to less than 53 wt. % of the 3,3′

-bis(halophthalimide),

from 47 to less than 85 wt. % of the 4,3′

-bis(halophthalimide) and

from more than 0 to less than 27 wt. % of the 4,4′

-bis(halophthalimide).

9. The composition of claim 1, further comprising an additive selected from impact modifiers, fillers, reinforcing agents, anti-oxidants, heat stabilizers, light stabilizers, ultraviolet light absorbers, plasticizers, lubricants, mold release agents, antistatic agents, colorants, blowing agents, flame retardants, anti-drip agents, and radiation stabilizers, and a combination thereof.

10. A method for the manufacture of the polyetherimide composition of claim 1, the method comprising reacting, in the presence of a catalytically active amount of a phase transfer catalyst, the alkali metal salt of a dihydroxy aromatic compound with the bis(halophthalimide) composition.

11. The method of claim 10, wherein a first portion of the alkali metal salt of the dihydroxy aromatic compound reacted with the bis(halophthalimide) composition to form a first polyetherimide having a first molecular weight;

and a second portion of the e alkali metal salt of the dihydroxy aromatic compound is added to first polyetherimide to form a second polyetherimide having a second molecular weight higher than the first molecular weight.

12. An article comprising the composition of claim 1.

13. The article of claim 12, selected from a sheet, film, multilayer sheet, multilayer film, molded part, extruded profile, coated part, and fiber.

14. The article of claim 13, wherein the article is a molded part having a thickness from 1 to 5 millimeters.

15. The article of claim 12, selected from a reflector, an optical lens, a fiber optic connector, and an adhesive.

16. A method of forming an article, comprising shaping, extruding, blow molding, or molding the composition of claim 1 to form the article.

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, 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

17. A polyetherimide of the formula

18. The polyetherimide of claim 17, comprising from more than 47 wt. % to less than 85 wt. % of the —

O—

Z—

O—

groups in the 3,4′

, and 4′

,3 positions.

19. The polyetherimide of claim 17, comprising

from 15 to less than 85 mol % of the of the —

O—

Z—

O—

groups in the 3,3′

position,

from more than 47 to less than 85 mol % of the O—

Z—

O—

groups in the 4,3′ and

3,4′

positions, and

from more than 0 to less than 27 mol % of the O—

Z—

O—

groups in the 4,4′

position.