High heat copolyimides, articles prepared therefrom, and methods of manufacturing copolyimide articles
View Patent ↗A copolyimide includes the reaction product of an aromatic dianhydride component including a substituted or unsubstituted pyromellitic dianhydride or a functional derivative thereof and an aromatic bis(ether phthalic anhydride) or a functional derivative thereof, and an organic diamine component comprising a substituted or unsubstituted phenylene diamine and a diaminodiphenyl sulfone. Articles and compositions including the copolyimides and methods of manufacturing a polyimide film are also described.
1. A copolyimide, comprising the reaction product of
an aromatic dianhydride component comprising, based on the total moles of the aromatic dianhydride component,
greater than 50 to 90 mole percent of a substituted or unsubstituted pyromellitic dianhydride or a functional derivative thereof; and
10 to less than 50 mole percent of an aromatic bis(ether phthalic anhydride) or a functional derivative thereof, of the formula
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 comprising at least one of the foregoing, and
the divalent bonds of the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions; and
an organic diamine component comprising, based on the total moles of the organic diamine component,
10 to 90 mole percent of a substituted or unsubstituted phenylene diamine; and
10 to 90 mole percent of a diaminodiphenyl sulfone; and
wherein the copolyimide exhibits at least one of the following properties:
a glass transition temperature greater than or equal to 210° C. as determined by differential scanning calorimetry;
an onset decomposition temperature of greater than or equal to 500° C., as determined by thermogravimetric analysis under nitrogen or air;
has a water uptake of less than or equal to 3.2% determined by comparing the difference in the weight of a polyimide film that has been immersed in water for 24 hours with the dry weight of the same polyimide film prior to immersion in water;
a coefficient of thermal expansion of 20 to 55 ppm/° C., as determined according to ASTM E 831; and
a transmission of at least 85% at one or more of 850 nm, 1310 nm, or 1550 nm as measured on an ultraviolet-visible/near infrared spectrophotometer using a 20 to 100 micrometer-thick film of the copolyimide.
2. The copolyimide of claim 1 , further having at least one of the following properties:
a weight average molecular weight of at least 15,000 Daltons;
a residual solvent content of less than 1000 parts per million by weight of the copolyimide;
a shift in melt viscosity of less than 30% over 30 minutes at 380° C. under a nitrogen atmosphere as measured in a small amplitude oscillatory time sweep rheology at a fixed angular frequency of 10 radians/second; and
a char yield of greater than 30 weight percent, as determined using thermogravimetric analysis under inert atmosphere of nitrogen.
3. The copolyimide of claim 1 , wherein the organic diamine component comprises meta-phenylene diamine and 3,3′-diaminodiphenyl sulfone.
4. The copolyimide of claim 1 , wherein the aromatic dianhydride component comprises pyromellitic dianhydride, 4,4′-bisphenol A dianhydride, 3,3′-bisphenol A dianhydride, or a combination comprising at least one of the foregoing.
5. The copolyimide of claim 1 , wherein
the aromatic dianhydride component comprises
greater than 50 to 70 mole percent pyromellitic dianhydride; and
30 to less than 50 mole percent of the aromatic bis(ether phthalic anhydride); and
the organic amine component comprises
10 to 90 mole percent 3,3′-diaminodiphenyl sulfone and
10 to 90 mole percent meta-phenylene diamine; and
the copolyimide has a glass transition temperature of greater than or equal to 250° C.
6. A method of manufacturing a polyimide film, the method comprising,
casting a solution comprising a copolyamic acid corresponding to the copolyimide of claim 1 and a liquid carrier on a substrate to provide a copolyamic acid film; and
curing the polyamic acid film to provide the polyimide film.
7. A method of manufacturing a polyimide film, the method comprising,
extruding a solution comprising a copolyamic acid solution corresponding to the copolyimide of claim 1 and a liquid carrier to provide a polyimide film.
8. The method of claim 6 , wherein the copolyamic acid is prepared by a method comprising contacting
an aromatic dianhydride component comprising, based on the total moles of the aromatic dianhydride component,
10 to 90 mole percent of a substituted or unsubstituted pyromellitic dianhydride or a functional derivative thereof; and
10 to 90 mole percent of an aromatic bis(ether phthalic anhydride) or a functional derivative thereof, of the formula
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 comprising at least one of the foregoing, and
the divalent bonds of the —O—Z—O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions; and
an organic diamine component comprising, based on the total moles of the organic diamine component,
10 to 90 mole percent of a substituted or unsubstituted phenylene diamine; and
10 to 90 mole percent of a diaminodiphenyl sulfone.
9. The method of claim 6 , wherein the liquid carrier is ortho-dichlorobenzene, dimethyl formamide, dimethyl acetamide, N-methylpyrrolidone, sulfolane, diphenyl sulfone, dimethyl sulfone, m-cresol, diphenyl ether, hexamethyl phosphoramide, dimethyl imidazole, dimethyl sulfoxide, tetramethylurea, N-methylpyrrolidone, veratrole, anisole, tetrahydrofuran, 1,4-dioxane, dimethyl carbonate, N-methyl-caprolactam, an aliphatic alcohol, water, or a combination comprising at least one of the foregoing.
10. The method of claim 6 , wherein the curing comprises thermal curing or vacuum imidization, or chemical imidization, wherein chemical imidization is conducted in the presence of a chemical imidization agent.
11. The method of claim 8 , wherein
the contacting is in the presence of an end capping agent;
the end capping agent comprises a monofunctional amine, a monofunctional anhydride, or a combination comprising at least one of the foregoing; and
the end capping agent is added at the beginning, during, or at the end of polymerization.
12. A polymer composition comprising,
1 to 99 weight percent of a thermoplastic polymer; and
1 to 99 weight percent of the copolyimide of claim 1 ,
wherein weight percent of each component is based on the total weight of the composition.
13. The polymer composition of claim 12 , wherein the thermoplastic polymer is a poly(ether ether ketone), a poly(ether ketone), a poly(ether ketone ketone), a poly(ketone ether ketone ketone), or a combination comprising at least one of the foregoing.
14. The polymer composition of claim 12 , further comprising an additive, wherein the additive is a particulate filler, reinforcing agent, lubricant, colorant, stabilizer, mold release agent, ultraviolet light absorber, or a combination comprising at least one of the foregoing.
15. An article comprising the copolyimide of claim 1 .
16. The article of claim 15 , wherein the article is an optical lens, sight glass, optical fiber connector, electrical connector, light-emitting diode reflector, printed circuit board substrate, reflector for automotive headlamp, component of a fuel system for a gasoline engine, a diesel engine, an aircraft jet engine, or an aircraft turboprop engine, a fuel bowl, an adhesive, or a fuel filter housing.
17. A method of forming the article of claim 15 , comprising shaping, extruding, or molding, the copolyimide of claim 1 .
18. The copolyimide of claim 1 , wherein the copolyimide exhibits all of the following properties:
a glass transition temperature greater than or equal to 210° C. as determined by differential scanning calorimetry;
an onset decomposition temperature of greater than or equal to 500° C., as determined by thermogravimetric analysis under nitrogen or air;
has a water uptake of less than or equal to 3.2% determined by comparing the difference in the weight of a polyimide film that has been immersed in water for 24 hours with the dry weight of the same polyimide film prior to immersion in water;
a coefficient of thermal expansion of 20 to 55 ppm/° C., as determined according to ASTM E 831; and
a transmission of at least 85% at one or more of 850 nm, 1310 nm, or 1550 nm as measured on an ultraviolet-visible/near infrared spectrophotometer using a 20 to 100 micrometer-thick film of the copolyimide.