Polycarbonate-polysiloxane copolymers, method of making, and articles formed therefrom

1. A copolycarbonate comprising

90 to 100 mol % of units derived from a cycloalkylidene-bridged alkyl-substituted bisphenol of the formula

wherein R a′ and R b′ are each independently C 1-12 alkyl, T is a C 5-16 cycloalkylene, or a C 5-16 cylcloalkylidene, and r and s are each independently 1 to 4;

2 to 35 wt % of units derived from a polysiloxane diol of the formulas

or a combination thereof, wherein Ar is a substituted or unsubstituted C 6-36 arylene group, each R is the same or different C 1-13 monovalent organic group, each R 6 is the same or different divalent C 1 -C 30 organic group, and E is an integer from 40 to 60; and

0 to 10 mol % of units derived from a dihydroxy aromatic compound of formula

wherein R a and R b are each independently halogen or C 1-12 alkyl group, X a is a C 1-18 organic group, p and q are each independently integers of 0 to 4, and the dihydroxy aromatic compound is not the same as the cycloalkylidene-bridged bisphenol or the polysiloxane diols; and

wherein each of the foregoing mole percents is based on the total moles of bisphenol of formula (1) and dihydroxy aromatic compound of formula (3) used to manufacture the copolycarbonate, and the weight percent is based on the total weight of the bisphenol of formula (1), polysiloxane diols of formula (2a) and/or (2b), and dihydroxy aromatic compound of formula (3) used to manufacture the copolycarbonate.

2. The copolycarbonate of claim 1 , wherein the cycloalkylidene-bridged alkyl-substituted bisphenol (1) is a cyclohexylidene bisphenol of the formula:

wherein R a′ and R b′ are each independently C 1-12 alkyl, R g is C 1-12 alkyl or halogen, r and s are each independently 1 to 4, and t is 0 to 10.

3. The copolycarbonate of claim 1 , wherein the copolycarbonate is derived from a composition that consists essentially of the cycloalkylidene-bridged alkyl-substituted bisphenol and at least one of the polysiloxane diols.

4. The copolycarbonate of claim 2 , wherein the copolycarbonate is derived from a composition that consists of the cyclohexylidene bisphenol and at least one of the polysiloxane diols.

5. The copolycarbonate of claim 2 , wherein R a′ and R b′ are each independently C 1-4 alkyl, R g is C 1-4 alkyl, r and s are each independently 1 to 2, and t is 0 to 5, and R a′ and R b′ are each disposed meta to the cycloalkylidene bridge.

6. The copolycarbonate claim 1 , wherein Ar is a substituted or unsubstituted C 6-12 arylene group, and each R is the same C 1-4 alkyl group.

7. The copolycarbonate of claim 1 , wherein the polysiloxane diol is of the formula:

wherein E has an average value of 2 to 100, each R is a C 1-3 alkyl group, each R 3 is independently a divalent C 2-8 aliphatic group, each M is the same or different and is a halogen, cyano, nitro, C 1-8 alkylthio, C 1-8 alkyl, C 1-8 alkoxy, C 2-8 alkenyl, C 2-8 alkenyloxy group, C 3-8 cycloalkyl, C 3-8 cycloalkoxy, C 6-10 aryl, C 6-10 aryloxy, C 7-12 arylalkyl, C 7-12 arylalkoxy, C 7-12 alkylaryl, or C 7-12 alkylaryloxy, and each n is independently 0 to 4.

8. The copolycarbonate of claim 7 , wherein M is bromo, chloro, a C 1-3 alkyl group, a C 1-3 alkoxy group, phenyl, chlorophenyl, or tolyl; R 3 is a dimethylene, trimethylene or tetramethylene group; and R is a C 1-8 alkyl, trifluoropropyl, cyanoalkyl, phenyl, chlorophenyl or tolyl.

9. The copolycarbonate of claim 7 , wherein R is methyl, a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl; M is methoxy, n is one, and R 3 is a divalent C 1 -C 3 aliphatic group.

10. The copolycarbonate of claim 1 , wherein p is 0 to 1, and X a is

wherein R c and R d are each independently hydrogen, C 1-12 alkyl, cyclic C 1-12 alkyl, C 7-12 arylalkyl, C 1-12 heteroalkyl, or cyclic C 7-12 heteroarylalkyl, and R e is a divalent C 1-12 hydrocarbon group.

11. The copolycarbonate of claim 10 , wherein p is 0 and R c and R d are each independently C 1-3 alkyl.

12. A copolycarbonate comprising

95 to 100 mol % of units derived from a cyclohexylidene bisphenol of the formula

wherein R a′ and R b′ are each independently C 1-3 alkyl, R g is C 1-3 alkyl or halogen, r and s are each independently 1 to 2, and t is 0 to 5;

10 to 35 wt % of units derived from a polysiloxane diol of the formulas

wherein each R is the same or different C 1-13 monovalent organic group, each R 3 is the same or different divalent C 1 -C 8 aliphatic group, M is bromo, chloro, a C 1-3 alkyl group, a C 1-3 alkoxy group, phenyl, chlorophenyl, or tolyl, and E is an integer from 40 to 60; , and n is independently 0 to 4; and

0 to 5 mol % of units derived from a dihydroxy aromatic compound of formula

wherein R a and R b are each independently halogen, X a is a C 1-18 alkylene group, a C 3-18 cycloalkylene group, or a fused C 6-18 cycloalkylene group p and q are each independently integers of 0 to 1, and the dihydroxy aromatic compound is not the same as the cyclohexylidene bisphenol or the polysiloxane diols.

13. The copolycarbonate of claim 12 , wherein R a′ and R b′ are each methyl and each disposed meta to the cycloalkylidene bridge, r and s are each 1, t is 0, R is methyl, a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl, M is methoxy, n is one, R 3 is a divalent C 1 -C 3 aliphatic group, p and q are 0, and X a is isopropylidene.

14. A method of manufacture of a polycarbonate copolymer, comprising

combining the components of claim 1 and 0 to 50% of the total amount of an end-capping agent in a biphasic solvent to provide a first reaction mixture;

adding sufficient caustic to the first combination to achieve a pH of 8.0 to 9.0;

reacting the pH-adjusted first reaction mixture with a carbonyl precursor in the presence of sufficient caustic to maintain a pH of 6.0 to 9.0, in the absence of any tertiary amine or phase transfer catalyst until 70 to 90% of the theoretical amount of carbonyl precursor required to react with all hydroxy groups is added, to provide a second reaction mixture;

adding 50 to 100% of the total amount of the end-capping agent to the second reaction mixture to provide a third reaction mixture; reacting the third reaction mixture with a carbonyl precursor in the presence of sufficient caustic to maintain a pH of 6.0 to 9.0 until 80 to 99% of the theoretical amount of carbonyl precursor required to react with all phenol groups has been delivered, to provide a fourth reaction mixture;

adding a tertiary amine catalyst to the fourth reaction mixture; and continuing the reaction in the presence of sufficient caustic to maintain a pH of 10 to 11.

15. The method of claim 14 , wherein additional amounts of a carbonyl precursor are added at pH 10 to 11 until the Mw of the polymer does not increase further.

16. A thermoplastic composition, comprising the copolycarbonate of claim 1 and an additive.

17. The thermoplastic composition of claim 16 , further comprising an additive, wherein the additive is an impact modifier, a filler, an ionizing radiation stabilizer, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet light absorber, a plasticizer, a lubricant, a mold release agent, an antistatic agent, a pigment, a dye, a flame retardant, an anti-drip agent, or a combination comprising at least one of the foregoing additives.

18. The thermoplastic composition of claim 16 , wherein an article having a thickness of 3.2 mm and molded from the thermoplastic composition has a NII strength of 20 to 100 Joules per meter (J/m), measured at 23° C. in accordance with ASTM D256-04.

19. The thermoplastic composition of claim 16 , wherein an article having a thickness of 3.2±0.12 mm and molded from the thermoplastic composition has a haze of less than 10%, measured in accordance with ASTM D1003-00.

20. The thermoplastic composition of claim 16 , wherein an article having a thickness of 3.2 mm and molded from the thermoplastic composition has a Dynatup Ductility total energy of 4 to 40 Joules as measured by ASTM D3763-02.

21. A method of manufacture of a thermoplastic composition, comprising blending the copolycarbonate of claim 1 with a polycarbonate or a polycarbonate polysiloxane copolymer to form a thermoplastic composition.

22. A method of manufacture of a thermoplastic composition, comprising blending the copolycarbonate of claim 1 with an additive to form a thermoplastic composition.

23. An article, comprising the thermoplastic composition of claim 16 .

24. The article of claim 23 , in the form of a syringe barrel, sample container, medicament containers, plastic vials, blood housings, filter housings, membrane housings, and plungers.

25. A method of manufacture of an article, comprising molding, extruding, or shaping the thermoplastic composition of claim 15 into an article.

26. The copolycarbonate of claim 1 , further comprising 0 to 10 mol % of units derived from a dihydroxy aromatic compound of formula (12):

wherein each R f is independently C 1-12 alkyl, or halogen, and u is 0 to 4.