High glass transition temperature polycarbonates derived from adamantane epoxides
Embodiments in accordance with the present invention relate generally to polycarbonate polymers having repeat units derived from adamantane epoxide monomers and methods of using such polymers and compositions containing them. The compositions thus formed are useful in a variety of optoelectronic device fabrications.
1. A polymer consisting of a repeat unit of formula (IV), said repeat unit is derived from a compound of formula (I) and carbon dioxide:
wherein:
represents a position at which the bonding takes place with another repeat unit;
each occurrence of R 1 and R 2 independently of each other selected from the group consisting of hydrogen, methyl, ethyl and phenyl; and
each occurrence of R 3 R 4 and R 5 independently of each other selected from the group consisting of hydrogen, methyl, ethyl and halogen.
2. The polymer according to claim 1 , wherein:
each occurrence of R 1 and R 2 independently represents hydrogen, methyl, ethyl or phenyl; and
each occurrence of R 3 , R 4 and R 5 independently represents hydrogen, methyl, ethyl or fluorine.
3. The polymer according to claim 1 , wherein said repeat unit of formula (IV) is derived from a compound selected from one or more of the following:
4. The polymer according to claim 1 , wherein the weight average molecular weight of said polymer is from about 1,000 to about 300,000.
5. The polymer according to claim 1 , wherein said polymer exhibits a glass transition temperature of at least about 100° C.
6. A process for making a polymer of formula (IV) according to claim 1 comprising:
reacting a compound of formula (I) with carbon dioxide in the presence of a ligand-supported metal catalyst:
wherein:
represents a position at which the bonding takes place with another repeat unit;
each occurrence of R 1 and R 2 independently of each other selected from the group consisting of hydrogen, methyl, ethyl and phenyl; and
each occurrence of R 3 R 4 and R 5 independently of each other selected from the group consisting of hydrogen, methyl, ethyl and halogen.
7. The process according to claim 6 which includes a halogenated solvent.
8. The process according to claim 6 , wherein the ligand-supported metal catalyst is selected from the group consisting of chromium, manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum and zinc.
9. The process according to claim 6 , wherein the catalyst is a cobalt metal complex of formulae (VI) or (VII):
wherein
R is methyl, ethyl, linear or branched C 3 -C 12 -alkyl, C 3 -C 12 -cycloalkyl and C 6 -C 10 -aryl; and
Y is halogen, acetate, trifluoroacetate, benzoate, tosylate, triflate, mesylate, C 6 F 5 CO 2 and azide.
10. The process according to claim 9 , wherein R is tert-butyl and Y is chlorine.
11. The process according to claim 6 , wherein it further comprises a co-catalyst, which is N,N-dimethylpyridin-4-amine.
12. A sacrificial polymer composition comprising:
a polymer according to claim 1 ;
a photoacid generator (PAG) or photobase generator (PBG) or mixtures thereof; and
a solvent.
13. The sacrificial polymer composition according to claim 12 , which further comprises a thermally activated acid generator (TAG).
14. The sacrificial polymer composition of claim 12 where the solvent is selected from anisole, n-butyl acetate (BuOAc), dimethylacetamide (DMAc), cyclopentanone, cyclohexanone, gamma butyrolactone (GBL), propyleneglycol-monomethylether acetate (PGMEA) and mixtures thereof.
15. The sacrificial polymer composition of claim 12 where the photoacid or photobase generator is selected from the following:
and mixtures in any combination thereof.
16. The sacrificial polymer composition of claim 12 , which further comprises optional additives selected from the group consisting of sensitizers, adhesion promoters, antioxidants, antioxidant synergists and fillers.
17. The sacrificial polymer composition of claim 16 , where said optional additives are selected from 1-chloro-4-propylthioxanthane (CPTX), isopropyl thioxanthone (ITX), phenothiazine, benzoquinone and 1,1,1-tris(hydroxymethyl)propane (THMP).
18. The sacrificial polymer composition of claim 12 where the photoacid generator (PAG) or photobase generator loading is from 0.15 parts per hundred polymer to 10 parts per hundred polymer, inclusive.
19. A polymer consisting of a repeat unit of formula (PAdEC), said repeat unit is derived from 2-(adamantan-1-yl)oxirane and carbon dioxide:
20. A sacrificial polymer composition comprising:
a polymer according to claim 19 ;
a photoacid generator (PAG) or photobase generator (PBG) or mixtures thereof; and
a solvent.