Thermoplastic polyimides, method for the manufacture thereof, and articles prepared therefrom

1. A polymer composition comprising a polyetherimide comprising repeating units of formula (1) and formula (2)

wherein

the repeating units of formula (1) are present in an amount of at least 10 mole %;

Z is independently at each occurrence derived from a biphenol;

Z′ is independently at each occurrence a group derived from

wherein R a and R b at each occurrence are each independently halogen, C 1-12 alkyl, C 2-12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy; p and q at each occurrence are each independently 0 to 4; R 13 at each occurrence is independently halogen or C 1-6 alkyl; c at each occurrence is independently 0 to 4; R g at each occurrence is independently halogen or C 1-12 alkyl, or two R g groups together with the carbon atoms to which they are attached form a four-, five, or six-membered cycloalkyl group; and t is 0 to 10; and

R is independently at each occurrence is a C 6-20 aromatic hydrocarbon 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 a halogenated derivative thereof;

wherein the polyetherimide has a Tg of greater than 200° C.

2. The polymer composition of claim 1 , wherein the polyetherimide has at least one of:

a weight average molecular weight of at least 20,000 grams per mole;

a maximum hydroxyl polymer endgroup content of 700 parts per million by weight; and

further wherein the polymer composition comprises less than 3000 part per million of a chloride, based on the total parts of polyetherimide.

3. The polymer composition of claim 1 , wherein the polyetherimide is prepared from a bis(halophthalimide) of the formula

wherein

each occurrence of X is independently fluoro, chloro, bromo, iodo, or nitro; and

R is independently at each occurrence is a C 6-20 aromatic hydrocarbon 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 a halogenated derivative thereof.

4. The polymer composition of claim 3 , wherein the polyetherimide is prepared by a method comprising contacting the bis(halophthalimide) composition and an alkali metal salt of a dihydroxy compound of the formula

M +− O—Z—O −+ M and M +− O—Z′—O −+ M;

under conditions effective to provide the polyetherimide,

wherein

M is an alkali metal;

Z is independently at each occurrence derived from a biphenol; and

Z′ is independently at each occurrence a group derived from

wherein R a and R b at each occurrence are each independently halogen, C 1-12 alkyl, C 2-12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy; p and q at each occurrence are each independently 0 to 4; R 13 at each occurrence is independently halogen or C 1-6 alkyl; c at each occurrence is independently 0 to 4; R g at each occurrence is independently halogen or C 1-12 alkyl, or two R g groups together with the carbon atoms to which they are attached form a four-, five, or six-membered cycloalkyl group; and t is 0 to 10.

5. The polymer composition of claim 3 , wherein the molar ratio of alkali metal salt of the dihydroxy compound to bis(halophthalimide) is from 0.9:1.0 to 1:0:0.9.

6. The polymer composition of claim 3 , wherein the contacting is in the presence of an endcapping agent.

7. The polymer composition of claim 1 , wherein Z is a group derived from 4,4′-biphenol, Z′ is a group derived from 6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane, 1,2-dihydroxybenzene, isophorone bisphenol, 1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane, dimethylindanone bisphenol, 3,3′-dimethylbisphenol cyclohexane, fluorenone bisphenol or a combination comprising at least one of the foregoing, and R is an m-phenylene group.

8. The polymer composition of claim 1 , wherein the polymer composition

comprises less than 2 weight percent of cyclic oligomers; or

has an onset decomposition temperature of greater than 500° C. as determined using thermogravimetric analysis in air; or

has a water uptake of less than 1 percent; or

has a coefficient of thermal expansion of 30 to 60 ppm/° C., as determined according to ASTM E 831.

9. The polymer composition of claim 1 , wherein the molar ratio of Z to Z′ is 30:70 to 70:30.

10. The polymer composition of claim 1 , wherein

Z is a group derived from 4,4′-biphenol;

Z′ is a group derived from 6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane; and

the molar ratio of Z to Z′ is 30:70 to 70:30; and

R is a meta-phenylene group.

11. The polymer composition of claim 1 ,

having a transparency of at least 82% at one or more of 850 nm, 1310 nm, and 1550 nm as determined on a 1.2 mm thick part; or

wherein the polyetherimide in molten form that has been exposed to a temperature of at least 380° C. for at least 5 minutes has a viscosity that is greater than or equal to 95% of the initial viscosity of the polyetherimide; or

wherein the polymer composition retains a melt stability that is at least 95% of the initial melt stability following exposure to a temperature of 400° C. for 30 minutes.

12. A method for the manufacturer of a polyetherimide composition, the method comprising reacting

an alkali metal salt of a dihydroxy aromatic compound of the formula

M +− O—Z—O −+ M and M +− O—Z′—O +− M

with a bis(halo)phthalimide, preferably in a molar ratio of 1.0:0.9 to 0.9:1.0, of the formula,

under conditions effective to provide the polyetherimide, and wherein in the foregoing formulas

M is an alkali metal,

Z is independently at each occurrence derived from a biphenol group,

Z′ is independently at each occurrence a group derived from 1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane, isophorone bisphenol (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), spirobiindane bisphenol, dimethylindanone bisphenol, 3,3′-dimethylbisphenol cyclohexane, or fluorenone bisphenol,

X is independently at each occurrence fluoro, chloro, bromo, iodo or nitro, and

R is independently at each occurrence a C 6-20 aromatic hydrocarbon group or a halogenated derivative thereof, a straight or branched chain C 2-20 alkylene group or a halogenated derivative thereof, a C 3-8 cycloalkylene group or halogenated derivative thereof.

13. The method of claim 12 , wherein the contacting is

in the presence of a monophenol or the corresponding alkali metal salt thereof; or

in the presence of a catalyst.

14. The method of claim 12 , wherein the polyetherimide composition comprises less than 1000 ppm of residual catalyst, based on the weight of a polyetherimide.

15. The method of claim 12 , wherein the polyetherimide composition has

a Tg of greater than 200° C.;

a weight average molecular weight of at least 20,000 grams per mole;

less than 3000 part per million of a chloride based on the total parts of polyetherimide; and

a maximum hydroxyl polymer endgroup content of 700 parts per million by weight.

16. A method for the manufacturer of a polyetherimide composition, the method comprising reacting an aromatic bis(ether phthalic anhydride) of formula (12) and (13)

with an aromatic diamine of the formula

H 2 N—R—NH 2

to provide a polyetherimide, wherein in the foregoing formulas

Z is independently at each occurrence derived from a biphenol group; and

Z′ is independently at each occurrence a group derived from 1,1-bis(4-hydroxyphenyl)-1-phenyl-ethane, isophorone bisphenol (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), spirobiindane bisphenol, dimethylindanone bisphenol, 3,3′-dimethylbisphenol cyclohexane, or fluorenone bisphenol;

R is independently at each occurrence a C 6-20 aromatic hydrocarbon 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 a halogenated derivative thereof.

17. The method of claim 12 , wherein R is a meta-phenylene group.

18. An article comprising the polymer composition of claim 1 .

19. The article of claim 18 , wherein

the article is an injection molded part, a film, a sheet, a multilayer sheet, a multilayer film, a multilayered laminate, a molded part, an extruded shape, a coated part, a pellet, a powder, a foam, a fiber, a flaked fiber, an extruded sheet, an extruded film, an extruded fiber, tubing, or an extruded stock shape.

20. A method of forming the article of claim 18 , comprising shaping, extruding, blow molding, injection molding, thermoforming, or laminating the polymer composition of claim 1 to form the article.