Polyarylene polymers
View Patent ↗Compositions of arylene oligomers and certain curing agents are useful to provide arylene polymer coatings having improved mechanical properties when cured in an oxygen-containing atmosphere. Methods of curing such compositions are also provided.
1. A composition comprising one or more curable arylene oligomers comprising as polymerized units one or more first monomers having two cyclopentadienone moieties and one or more second monomers having two or more alkyne moieties; one or more curing agents of the formula
wherein Ar 4 , Ar 5 and Ar 6 are independently aromatic moieties having from 1 to 3 aromatic rings, each of which may be unsubstituted or substituted; wherein in at least one of Ar 4 , Ar 5 and Ar 6 is substituted with hydroxyl; and one or more organic solvents.
2. The composition of claim 1 wherein the one or more first monomers have the structure shown in formula (1)
wherein each R 1 is independently chosen from H, C 1-6 alkyl, phenyl, or substituted phenyl; and Ar 1 is an aromatic moiety.
3. The composition of claim 2 wherein each R 1 is phenyl.
4. The composition of claim 1 wherein the one or more second monomers are chosen from compounds of formula (5) and formula (6)
wherein a is an integer from 0 to 4; b is 2 or 3; c is 2 or 3; each R 6 is independently chosen from H, Si(R 8 ) 3 , C 1-10 alkyl, C 1-10 alkoxy, C 7-15 aralkyl, C 6-10 aryl, and substituted C 6-10 aryl; each R 7 is independently chosen from H, C 1-10 alkyl, C 1-10 alkoxy, C 7-15 aralkyl, C 6-10 aryl, and substituted C 6-10 aryl; each R 8 is independently chosen from H, halogen, hydroxyl, C 1-10 alkyl, C 1-10 alkoxy, C 7-15 aralkyl, C 7-15 aralkoxy, C 6-10 aryl, C 6-20 aryloxy, and substituted C 6-10 aryl; and Ar 3 is C 6-10 aryl.
5. The composition of claim 1 , wherein each of Ar 4 , Ar 5 and Ar 6 is unsubstituted or substituted phenyl or naphthyl.
6. The composition of claim 1 , wherein the one or more curing agents have the formula
wherein each R 16 , R 17 and R 18 is independently chosen from hydroxy, C 1-20 alkyl, C 1-20 alkoxy, halo, C 1-20 haloalkyl, C 1-20 carboxy, amino, C 1-20 acylamino, and OR 15 ; R 15 is an organic radical having from 1 to 25 carbon atoms; a and b are each integers from 0 to 3; and c is an integer from 0 to 2.
7. A method of curing an arylene oligomer comprising:
disposing a composition comprising one or more curable arylene oligomers comprising as polymerized units one or more first monomers having two cyclopentadienone moieties and one or more second monomers having two or more alkyne moieties; one or more curing agents of the formula
wherein Ar 4 , Ar 5 and Ar 6 are independently aromatic moieties having from 1 to 3 aromatic rings, each of which may be unsubstituted or substituted; wherein in at least one of Ar 4 , Ar 5 and Ar 6 is substituted with hydroxyl; and one or more organic solvents on a substrate surface; at least partially removing the one or more organic solvents; and curing the one or more arylene oligomers in air to form a cured arylene coating on the substrate.
8. The method of claim 7 , wherein the one or more curing agents have the formula
wherein each R 16 , R 17 and R 18 is independently chosen from hydroxy, C 1-20 alkyl, C 1-20 alkoxy, halo, C 1-20 haloalkyl, C 1-20 carboxy, amino, C 1-20 acylamino, and OR 15 ; R 15 is an organic radical having from 1 to 25 carbon atoms; a and b are each integers from 0 to 3; and c is an integer from 0 to 2.
9. A method of forming a coated inorganic film comprising:
providing an inorganic film; coating a layer of a composition comprising one or more curable arylene oligomers comprising as polymerized units one or more first monomers having two cyclopentadienone moieties and one or more second monomers having two or more alkyne moieties; one or more curing agents of the formula
wherein Ar 4 , Ar 5 and Ar 6 are independently aromatic moieties having from 1 to 3 aromatic rings, each of which may be unsubstituted or substituted; wherein in at least one of Ar 4 , Ar 5 and Ar 6 is substituted with hydroxyl; and one or more organic solvents on a surface of the inorganic film; removing the one or more organic solvents from the coating layer; curing the coating layer in air to form a coated inorganic film.
10. The method of claim 9 further comprising disposing a protective film on the coated inorganic film.
11. The method of claim 9 wherein the inorganic film is transparent.
12. The method of claim 9 wherein the inorganic film is provided from a roll.
13. The method of claim 9 , wherein the one or more curing agents have the formula
wherein each R 16 , R 17 and R 18 is independently chosen from hydroxy, C 1-20 alkyl, C 1-20 alkoxy, halo, C 1-20 haloalkyl, C 1-20 carboxy, amino, C 1-20 acylamino, and OR 15 ; R 15 is an organic radical having from 1 to 25 carbon atoms; a and b are each integers from 0 to 3; and c is an integer from 0 to 2.