Polycarbonate resins method of manufacture, and articles formed therefrom
Disclosed herein is a polycarbonate comprising a terminal olefin group of the formula wherein R 1 is a C 1 -C 40 hydrocarbon that can be unsubstituted or substituted with a halogen, olefin, ether, ketone, or C 4 -C 30 polyoxyalkylene functionality in which the alkylene groups contain 2 to 6 carbon atoms, R 2 to R 4 are each independently a hydrogen or a C 1 -C 40 hydrocarbon that can be unsubstituted or substituted with a halogen, olefin, ether, ketone, or a C 4 -C 30 polyoxyalkylene functionality in which the alkylene groups contain 2 to 6 carbon atoms, and optionally wherein any two of R 1 to R 4 together form a monocyclic, bicyclic, or tricyclic ring system optionally substituted with a heteroatom in each ring.
1. A polycarbonate, wherein the polycarbonate comprises a terminal olefin group of the formula
wherein
R 1 is a C 1 -C 40 hydrocarbon that can be unsubstituted or substituted with a halogen, olefin, ether, or a C 4 -C 30 polyoxyalkylene functionality in which the alkylene groups contain 2 to 6 carbon atoms, and
R 2 to R 4 are each independently a hydrogen or a C 1 -C 40 hydrocarbon that can be unsubstituted or substituted with halogen, olefin, ether, or C 4 -C 30 polyoxyalkylene functionality in which the alkylene groups contain 2 to 6 carbon atoms,
optionally wherein any two of R 1 to R 4 together form a monocyclic, bicyclic, or tricyclic ring system optionally substituted with a heteroatom in the ring; and
wherein the polycarbonate comprising the terminal olefin group is the reaction product of a carbonate and a compound of the formula
or a combination comprising at least one of the foregoing formulas at a temperature and for a time effective to form the terminal olefin group.
2. The polycarbonate of claim 1 , wherein R 2 and R 3 are each a hydrogen.
3. The polycarbonate of claim 1 , wherein R 3 and R 4 are each a hydrogen.
4. The polycarbonate of claim 1 , wherein R 1 and R 4 together form a monocyclic, bicyclic, or tricyclic group optionally substituted with a sulfur, nitrogen, oxygen, or a combination comprising at least one of the foregoing atoms.
5. The polycarbonate of claim 1 , wherein R 1 and R 4 together form a bicyclic ring system wherein each ring is substituted with one oxygen atom, and R 2 and R 3 are each a hydrogen.
6. The polycarbonate of claim 1 , wherein
R 1 is a C 1 -C 40 alkylene, C 3 -C 30 cycloalkylene, C 6 -C 30 arylene, C 2 -C 30 alkenylene, C 7 -C 30 arylalkylene, C 7 -C 30 alkylarylene, or C 8 -C 30 arylalkenylene, and
R 2 to R 4 are each independently a hydrogen, C 1 -C 20 alkyl, C 3 -C 8 cycloalkyl, C 6 -C 12 aryl, C 2 -C 12 alkenyl, C 7 -C 13 arylalkyl, C 7 -C 13 alkylaryl, or C 8 -C 12 arylalkenyl.
7. The polycarbonate of claim 6 , wherein
R 1 is a C 1 -C 40 alkylene, and
R 2 to R 4 are each independently a hydrogen, C 1 -C 20 alkyl, or C 2 -C 12 alkenyl.
8. The polycarbonate of claim 7 , wherein R 2 and R 3 are each a hydrogen, or R 3 and R 4 are each a hydrogen.
9. The polycarbonate of claim 1 , wherein the polycarbonate comprises 0.01 mole % to 5 mole % of the terminal olefin groups.
10. The polycarbonate of claim 1 , where the polycarbonate comprises carbonate units derived from isosorbide.
11. The polycarbonate of claim 1 , wherein the polycarbonate comprises carbonate units derived from bisphenol A and/or resorcinol.
12. The polycarbonate of claim 1 , further comprising ester units of the formula
wherein E is a C 2-60 alkylene, a C 6-20 cycloalkylene, a C 6-20 arylene, or a C 4 -C 30 polyoxyalkylene in which the alkylene groups contain 2 to 6 carbon atoms, and T is a C 2-60 alkylene, a C 6-20 cycloalkylene, a C 6-20 alkylarylene, or a C 6-20 arylene.
13. The polycarbonate of claim 12 , wherein T is of the formula
wherein m and m′ are independently 0 to 38, n and n′ are independently 0 to 38, and the sum of (m +m′+n +n′) is 8 to 38.
14. A polycarbonate that is the reaction product of the polycarbonate comprising the terminal olefin group of claim 1 with a reactive agent to form a terminal group of the formula
wherein each X′ is independently a polymer, an oligomer, a compatibilizer, a crosslinker, an ultraviolet light stabilizer, a thermal stabilizer, a mold release agent, a gamma-stabilizer, a flame retardant, or an antioxidant, and one X′ is optionally a hydrogen.
15. An article comprising the polycarbonate of claim 14 .
16. A thermoplastic composition comprising the polycarbonate of claim 14 .
17. A method for the manufacture of an olefin group-terminated polycarbonate, the method comprising:
melt reacting a carbonate and a compound of the formula:
or a combination comprising at least one compound of the foregoing formulas, wherein
R 1 is a C 1 -C 40 hydrocarbon that can be unsubstituted or substituted with a halogen, olefin, ether, or C 4 -C 30 polyoxyalkylene functionality in which the alkylene groups contain 2 to 6 carbon atoms,
R 2 to R 4 are each independently a hydrogen or a C 1 -C 40 hydrocarbon that can be unsubstituted or substituted with a halogen, olefin, ether, or C 4 -C 30 polyoxyalkylene functionality in which the alkylene groups contain 2 to 6 carbon atoms,
R is a C 1-22 hydrocarbon, and
optionally wherein any two of R 1 to R 4 together form a monocyclic, bicyclic, or tricyclic ring system optionally substituted with a heteroatom in the ring,
at a temperature and for a time effective to form the olefin group-terminated polycarbonate.
18. The method of claim 17 , wherein the melt reacting is at a temperature greater than 210° C.
19. The method of claim 17 , wherein the melt reacting is by an extrusion, melt mixing, injection molding, or compression molding process.
20. The method of claim 17 , wherein the 1 H NMR spectrum of the olefin group-terminated polycarbonate comprises a broad NMR resonance centered at a chemical shift of between 6.4 ppm and 6.6 ppm and wherein the resonance is absent in the 1 H NMR spectrum of the polycarbonate.
21. The method of claim 17 , wherein R 2 and R 3 are each a hydrogen.
22. The method of claim 17 , wherein R 3 and R 4 are each a hydrogen.
23. The method of claim 17 , wherein R 1 and R 4 together form a monocyclic, bicyclic, or tricyclic group optionally substituted with a sulfur, nitrogen, oxygen, or a combination comprising at least one of the foregoing atoms.
24. The method of claim 17 , wherein R 1 and R 4 together form a bicyclic ring system wherein each ring is substituted with one oxygen atom, and R 2 and R 3 are each a hydrogen.
25. The method of claim 17 , wherein
R 1 is a C 1 -C 40 alkylene, C 3 -C 30 cycloalkylene, C 6 -C 30 arylene, C 2 -C 30 alkenylene, C 7 -C 30 arylalkylene, C 7 -C 30 alkylarylene, or C 8 -C 30 arylalkenylene, and
R 2 to R 4 are each independently a hydrogen, C 1 -C 20 alkyl, C 3 -C 8 cycloalkyl, C 6 -C 12 aryl, C 2 -C 12 alkenyl, C 7 -C 13 arylalkyl, C 7 -C 13 alkylaryl, or C 8 -C 12 arylalkenyl.
26. The method of claim 25 , wherein
R 1 is a C 1 -C 40 alkylene, and
R 2 to R 4 are each independently a hydrogen, C 1 -C 20 alkyl, or C 2 -C 12 alkenyl.
27. The method of claim 26 , wherein R 2 and R 3 are each a hydrogen, or R 3 and R 4 are each a hydrogen.
28. The method of claim 17 , wherein the polycarbonate comprises 0.01 mole % to 5 mole % of the terminal olefin groups.
29. The method of claim 17 , wherein the compound or compounds of the formula:
reacts with a carbonate group on a previously polymerized polycarbonate.
30. The method of claim 17 , further comprising reacting a terminal olefin group of the olefin-terminated polycarbonate with a reactive agent that is a polymer, an oligomer, a compatibilizer, a crosslinker, an ultraviolet light stabilizer, a thermal stabilizer, a mold release agent, a gamma-stabilizer, a flame retardant, or an antioxidant.
31. The method of claim 17 , further comprising reacting a terminal olefin group of the olefin-terminated polycarbonate with a reactive agent to form a terminal group of the formula
wherein each X′ is independently a polymer, an oligomer, a compatibilizer, a crosslinker, an ultraviolet light stabilizer, a thermal stabilizer, a mold release agent, a gamma-stabilizer, a flame retardant, or an antioxidant, and one X′ is optionally a hydrogen.
32. The polycarbonate of claim 14 , wherein one X′ is a crosslinker.