Process to make polycarbonate from bismethylsalicylcarbonate (BMSC)
View Patent ↗The present invention relates to a method of preparing polycarbonate comprising the steps of: (i) introducing to an extruder through a feed port a plurality of reaction components comprising a polycarbonate oligomer, an activated carbonate residue, and a transesterification catalyst, wherein the extruder comprises the feed port, a first back vent port, and a polycarbonate exit port, wherein the feed port is located between the first back vent port and the polycarbonate exit port, and wherein the resistance to flow of the reaction components from the feed port to the first back vent port is less than or equal to the resistance to flow of the reaction components from the feed port to the polycarbonate exit port; and (ii) extruding the reaction components at one or more temperatures in a range between 100° C. and 400° C., wherein during the extrusion of the reaction components, activated carbonate residue is removed through the first back vent port, thereby preparing a polycarbonate.
1. A method for preparing polycarbonate wherein the method comprises the steps of,
(i) introducing to an extruder through a feed port a plurality of reaction components comprising a polycarbonate oligomer, an activated carbonate residue, and a transesterification catalyst, wherein the extruder comprises the feed port, a first back vent port, and a polycarbonate exit port, wherein the feed port is located between the first back vent port and the polycarbonate exit port, and wherein the resistance to flow of the reaction components from the feed port to the first back vent port is less than or equal to the resistance to flow of the reaction components from the feed port to the polycarbonate exit port, and
(ii) extruding the reaction components at one or more temperatures in a range between 100° C. and 400° C., wherein during the extrusion of the reaction components, activated carbonate residue is removed through the first back vent port,
thereby preparing a polycarbonate.
2. The method of claim 1 , wherein no element is located between the feed port and the first back vent port that restricts the flow of the reaction components from the feed port to the first back vent port.
3. The method of claim 1 , wherein no active element is located between the feed port and the first back vent port that restricts the flow of the reaction components from the feed port to the first back vent port.
4. The method of claim 1 , wherein the extruder further comprises a front vent port located between the feed port and the polycarbonate exit port, wherein during the extrusion of the reaction components, activated carbonate residue is removed through the front vent port.
5. The method of claim 1 , wherein the polycarbonate comprises polycarbonate repeat units derived from more than one dihydroxy aromatic compound.
6. The method of claim 1 , wherein the activated carbonate residue comprises from 1% to 70% by weight of the total weight of the reaction components introduced to the extruder.
7. The method of claim 1 , wherein the activated carbonate residue comprises at least one ester-substituted phenol having structure I,
wherein R 1 is a C 1 –C 20 alkyl group, C 4 –C 20 cycloalkyl group, or C 4 –C 20 aryl group; R 2 is independently at each occurrence a halogen atom, cyano group, nitro group, C 1 –C 20 alkyl group, C 4 –C 20 cycloalkyl group, C 4 –C 20 aryl group, C 1 –C 20 alkoxy group, C 4 –C 20 cycloalkoxy group, C 4 –C 20 aryloxy group, C 1 –C 20 alkylthio group, C 4 –C 20 cycloalkylthio group, C 4 –C 20 arylthio group, C 1 –C 20 alkylsulfinyl group, C 4 –C 20 cycloalkylsulfinyl group, C 4 –C 20 arylsulfinyl group, C 1 –C 20 alkylsulfonyl group, C 4 –C 20 cycloalkylsulfonyl group, C 4 –C 20 arylsulfonyl group, C 1 –C 20 alkoxycarbonyl group, C 4 –C 20 cycloalkoxycarbonyl group, C 4 –C 20 aryloxycarbonyl group, C 2 –C 60 alkylamino group, C 6 –C 60 cycloalkylamino group, C 5 –C 60 arylamino group, C 1 –C 40 alkylaminocarbonyl group, C 4 –C 40 cycloalkylaminocarbonyl group, C 4 –C 40 arylaminocarbonyl group, or C 1 –C 20 acylamino group; and b is an integer 0–4.
8. The method of claim 7 , wherein the activated carbonate residue comprises methyl salicylate.
9. The method of claim 7 , wherein the reaction components further comprise a solvent selected from the group consisting of a halogenated aromatic solvent, a halogenated aliphatic solvent, a non-halogenated aromatic solvent, and a non-halogenated aliphatic solvent.
10. The method of claim 9 , wherein the solvent is ortho-dichlorobenzene.
11. The method of claim 1 , wherein the reaction components further comprise a monofunctional phenol chainstopper.
12. The method of claim 11 , wherein the chainstopper is p-cumylphenol.
13. The method of claim 1 , wherein the extruder has a screw speed, the reaction components being introduced into the extruder at a feed rate, the feed rate and the screw speed having a ratio, the extruder being operated such that the ratio of feed rate in pounds per hour to the screw speed expressed in revolutions per minute falls within a range of from 0.01 to 100.
14. The method of claim 13 , wherein the screw speed is in a range between 50 and 1,200 revolutions per minute.
15. The method of claim 1 , wherein the extruder is selected from the group consisting of a co-rotating intermeshing double screw extruder, a counter-rotating non-intermeshing double screw extruder; a single screw reciprocating extruder, a single screw non-reciprocating extruder, and a multiple screw extruder.
16. The method of claim 1 , wherein the back vent port port is operated at or below atmospheric pressure.
17. The method of claim 1 , further comprising the steps,
(i) heating the reaction components to a temperature greater than the boiling point of the activated carbonate residue, the boiling point being the boiling point of the activated carbonate residue at a flash pressure, the heating being carried out at a feed pressure, the feed pressure being greater than the flash pressure to provide superheated reaction components, and
(ii) flashing the superheated reaction components to the extruder at the flash pressure through at least one pressure control valve.
18. The method of claim 17 , wherein the extruder is selected from the group consisting of a co-rotating intermeshing double screw extruder, a counter-rotating non-intermeshing double screw extruder, a single screw reciprocating extruder, a single screw non-reciprocating extruder, and a multiple screw extruder.
19. The method of claim 17 , wherein the first back vent port is operated at the flash pressure which is lower than that of the feed pressure.
20. The method of claim 19 , wherein the ratio of (feed pressure/the pressure of the first back vent port) is in a range of greater than 0.01 and less than 1.
21. The method of claim 20 , wherein the ratio of (feed pressure/the pressure of the first back vent port) is in a range of greater than 0.1 and less than 1.
22. The method of claim 1 , further comprising the step of removing a product polycarbonate from the extruder.
23. The method of claim 22 , wherein the product polycarbonate is introduced into a second extruder, the second extruder comprising a vent port, and the second extruder being operated at a temperature in a range between 100° C. and 400° C., wherein during the extrusion of the product polycarbonate, activated carbonate residue is removed through the vent port.
24. The method of claim 23 , wherein the second extruder is selected from the group consisting of a co-rotating intermeshing double screw extruder, a counter-rotating non-intermeshing double screw extruder, a single screw reciprocating extruder, and a single screw non-reciprocating extruder.
25. The method of claim 23 , wherein the second extruder has a screw speed, the polycarbonate being introduced into the second extruder at a feed rate, the feed rate and the screw speed having a ratio, the second extruder being operated such that the ratio of feed rate in pounds per hour to the screw speed expressed in revolutions per minute falls within a range of from 0.01 to 100.
26. The method of claim 25 , wherein the screw speed of the second extruder is in a range between 50 and 1,200 revolutions per minute.
27. The method of claim 1 , wherein the method further comprises the steps of:
(i) forming a reaction mixture comprising at least one dihydroxy compound, an activated carbonate, and a transesterification catalyst, and
(ii) heating the reaction mixture at a temperature in a range between 100° C. and 300° C. to provide a plurality of reaction components comprising a polycarbonate oligomer, an activated carbonate residue, and a transesterification catalyst.
28. The method of claim 27 , wherein the method further comprises the step of removing activated carbonate residue from the reaction components prior to introduction to the extruder.
29. The method of claim 28 , wherein the step of removing activated carbonate residue from the reaction components prior to introduction to the extruder is accomplished by the use of a flash tank.
30. The method of claim 28 , wherein the step of removing activated carbonate residue from the reaction components prior to introduction to the extruder is accomplished by heating the oligomer solution and evaporating activated carbonate residue therefrom.
31. The method of claim 1 , wherein the reaction components are introduced to the extruder by the use of a side feeder, wherein the side feeder comprises a vent wherein activated carbonate residue is removed from the reaction components by the vent.
32. The method of claim 1 , wherein the extruder further comprises a second back vent port located further away from the feed port than the first back vent port wherein the second back vent port is operated at or below atmospheric pressure.
33. The method of claim 32 , wherein the restriction of flow from the feed port to the second back vent port is greater than the restriction of flow from the feed port to the polycarbonate exit port.
34. A method for preparing polycarbonate wherein the method comprises the steps of,
(i) forming a reaction mixture comprising at least one dihydroxy compound, an activated carbonate, and a transesterification catalyst,
(ii) heating the reaction mixture at a temperature in a range between 100° C. and 300° C. to provide the reaction components comprising a polycarbonate oligomer, an activated carbonate residue, and a transesterification catalyst,
(iii) removing activated carbonate residue from the reaction components prior to introduction to an extruder,
(iv) heating the reaction components to a temperature greater than the boiling point of the activated carbonate residue, the boiling point being the boiling point of the activated carbonate residue at a flash pressure, the heating being carried out at a feed pressure, the feed pressure being greater than the flash pressure to provide superheated reaction components,
(v) flashing the superheated reaction components to the extruder at the flash pressure through at least one pressure control valve feed port, wherein the extruder comprises the feed port, a first back vent port, and a polycarbonate exit port, wherein the feed port is located between the first back vent port and the polycarbonate exit port, and wherein the resistance to flow of the reaction components from the feed port to the first back vent port is less than or equal to the resistance to flow of the reaction components from the feed port to the polycarbonate exit port, and
(vi) extruding the reaction components at one or more temperatures in a range between 100° C. and 400° C., wherein during the extrusion of the reaction components activated carbonate residue is removed through the first back vent port,
thereby preparing a polycarbonate.
35. The method of claim 34 , wherein the extruder further comprises a front vent port located between the feed port and the polycarbonate exit port, wherein during the extrusion of the reaction components, activated carbonate residue is removed through the front vent port.
36. The method of claim 34 , wherein the polycarbonate comprises polycarbonate repeat units derived from more than one dihydroxy aromatic compound.
37. The method of claim 34 , wherein the activated carbonate residue comprises from 1% to 70% by weight of the total weight of the reaction components introduced to the extruder.
38. The method of claim 34 , wherein the activated carbonate residue comprises at least one ester-substituted phenol having structure I,
wherein R 1 is a C 1 –C 20 alkyl group, C 4 –C 20 cycloalkyl group, or C 4 –C 20 aryl group; R 2 is independently at each occurrence a halogen atom, cyano group, nitro group, C 1 –C 20 alkyl group, C 4 –C 20 cycloalkyl group, C 4 –C 20 aryl group, C 1 –C 20 alkoxy group, C 4 –C 20 cycloalkoxy group, C 4 –C 20 aryloxy group, C 1 –C 20 alkylthio group, C 4 –C 20 cycloalkylthio group, C 4 –C 20 arylthio group, C 1 –C 20 alkylsulfinyl group, C 4 –C 20 cycloalkylsulfinyl group, C 4 –C 20 arylsulfinyl group, C 1 –C 20 alkylsulfonyl group, C 4 –C 20 cycloalkylsulfonyl group, C 4 –C 20 arylsulfonyl group, C 1 –C 20 alkoxycarbonyl group, C 4 –C 20 cycloalkoxycarbonyl group, C 4 –C 20 aryloxycarbonyl group, C 2 –C 60 alkylamino group, C 6 –C 60 cycloalkylamino group, C 5 –C 60 arylamino group, C 1 –C 40 alkylaminocarbonyl group, C 4 –C 40 cycloalkylaminocarbonyl group, C 4 –C 40 arylaminocarbonyl group, or C 1 –C 20 acylamino group; and b is an integer 0–4.
39. The method of claim 38 , wherein the activated carbonate residue comprises methyl salicylate.
40. The method of claim 38 , wherein the reaction components further comprise a solvent selected from the group consisting of a halogenated aromatic solvent, a halogenated aliphatic solvent, a non-halogenated aromatic solvent, and a non-halogenated aliphatic solvent.
41. The method of claim 40 , wherein the solvent is ortho-dichlorobenzene.
42. The method of claim 34 , wherein the reaction components further comprise a monofunctional phenol chainstopper.
43. The method of claim 42 , wherein the chainstopper is p-cumylphenol.
44. The method of claim 34 , wherein the extruder has a screw speed, the reaction components being introduced into the extruder at a feed rate, the feed rate and the screw speed having a ratio, the extruder being operated such that the ratio of feed rate in pounds per hour to the screw speed expressed in revolutions per minute falls within a range of from 0.01 to 100.
45. The method of claim 44 , wherein the screw speed is in a range between 50 and 1,200 revolutions per minute.
46. The method of claim 34 , wherein the extruder is selected from the group consisting of a co-rotating intermeshing double screw extruder, a counter-rotating non-intermeshing double screw extruder; a single screw reciprocating extruder, a single screw non-reciprocating extruder, and a multiple screw extruder.
47. The method of claim 34 , wherein the first back vent port is operated at or below atmospheric pressure.
48. The method of claim 34 , wherein the first back vent port is operated at a pressure lower than that of the feed pressure.
49. The method of claim 48 , wherein the ratio of (feed pressure/the pressure of the first back vent port) is in a range of greater than 0.01 and less than 1.
50. The method of claim 49 , wherein the ratio of (feed pressure/the pressure of the first back vent port) is in a range of greater than 0.1 and less than 1.
51. The method of claim 34 , further comprising the step of removing a product polycarbonate from the extruder.
52. The method of claim 51 , wherein the product polycarbonate is introduced into a second extruder, the second extruder comprising a vent port, and the second extruder being operated at a temperature in a range between 100° C. and 400° C., wherein during the extrusion of the product polycarbonate activated carbonate residue is removed through the vent port.
53. The method of claim 52 , wherein the second extruder is selected from the group consisting of a co-rotating intermeshing double screw extruder, a counter-rotating non-intermeshing double screw extruder, a single screw reciprocating extruder, and a single screw non-reciprocating extruder.
54. The method of claim 52 , wherein the second extruder has a screw speed, the polycarbonate being introduced into the second extruder at a feed rate, the feed rate and the screw speed having a ratio, the second extruder being operated such that the ratio of feed rate in pounds per hour to the screw speed expressed in revolutions per minute falls within a range of from 0.01 to 100.
55. The method of claim 54 , wherein the screw speed of the second extruder is in a range between 50 and 1,200 revolutions per minute.
56. The method of claim 34 , wherein the step of removing activated carbonate residue from the reaction components prior to introduction to the extruder is accomplished by the use of a flash tank.
57. The method of claim 34 , wherein the step of removing activated carbonate residue from the reaction components prior to introduction to the extruder is accomplished by heating the oligomer solution and evaporating activated carbonate residue therefrom.
58. The method of claim 34 , wherein the reaction components are introduced to the extruder by the use of a side feeder, wherein the side feeder comprises a vent wherein activated carbonate residue is removed from the reaction components by the vent.
59. The method of claim 34 , wherein the extruder further comprises a second back vent port located further away from the feed port than the first back vent port wherein the second back vent port is operated at or below atmospheric pressure.
60. A molded article comprising polycarbonate formed by the steps of,
(a) preparing a polycarbonate by,
(i) introducing to an extruder through a feed port a plurality of reaction components comprising a polycarbonate oligomer, an activated carbonate residue, and a transesterification catalyst, wherein the extruder comprises the feed port, a first back vent port, and a polycarbonate exit port, wherein the feed port is located between the first back vent port and the polycarbonate exit port, and wherein the resistance to flow of the reaction components from the feed port to the first back vent port is less than or equal to the resistance to flow of the reaction components from the feed port to the polycarbonate exit port, and
(ii) extruding the reaction components at one or more temperatures in a range between 100° C. and 400° C., wherein during the extrusion of the reaction components, activated carbonate residue is removed through the first back vent port, thereby forming a polycarbonate, and
(b) forming a molded article from the polycarbonate.
61. A method for making a molded article formed from polycarbonate produced by the method comprising the steps of:
(a) preparing a polycarbonate by,
(i) introducing to an extruder through a feed port a plurality of reaction components comprising a polycarbonate oligomer, an activated carbonate residue, and a transesterification catalyst, wherein the extruder comprises the feed port, a first back vent port, and a polycarbonate exit port, wherein the feed port is located between the first back vent port and the polycarbonate exit port, and wherein the resistance to flow of the reaction components from the feed port to the first back vent port is less than or equal to the resistance to flow of the reaction components from the feed port to the polycarbonate exit port, and
(ii) extruding the reaction components at one or more temperatures in a range between 100° C. and 400° C., wherein during the extrusion of the reaction components, activated carbonate residue is removed through the first back vent port, thereby forming a polycarbonate, and
(b) forming a molded article from the polycarbonate.