Method of producing high molecular weight polymer
View Patent ↗The present invention provides methods of producing high molecular weight polymer. A method of forming polycarbonate includes the step of combining in a reaction mixture a diaryl carbonate, a transesterification catalyst, an aliphatic dihydroxy compound, and a diacid compound in a reactor system. The temperature and pressure of the reactor system are adjusted to a first reactor setpoints and the reaction mixture is monitored to detect initiation of the exothermic oligomerization reaction. The reactor setpoint are adjusted to second reactor setpoints after detection of initiation of the exothermic oligomerization reaction. The reactor system is maintained at the second reactor setpoints to allow the reaction mixture to react to form an oligomer mixture. The oligomer mixture is then introduced to a polymerization reactor system operating under melt polymerization conditions sufficient to polymerize the oligomer mixture to a Mw of at least 9,000 g/mol (PC) and to remove the phenolic byproduct from the oligomer mixture to form polycarbonate.
1. A method of forming polycarbonate comprising the steps of:
(a) introducing to a reactor system a reaction mixture comprising a diaryl carbonate, a transesterification catalyst, an aliphatic dihydroxy compound, and a diacid compound,
(b) adjusting the temperature of the reactor system to a first reactor temperature setpoint and adjusting the pressure of the reactor system to a first reactor pressure setpoint between 0.7 bar and 1.2 bar, wherein the first reactor temperature setpoint is selected such that:
(i) it is sufficiently high to provide a molten reaction mixture,
(ii) it is sufficiently high to initiate an exothermic oligomerization reaction in the reaction mixture to form a polycarbonate oligomer and a phenolic byproduct, and
(iii) it is below the boiling point of the phenolic byproduct at the first reactor pressure,
wherein during step (b) the reaction mixture is monitored to detect initiation of the exothermic oligomerization reaction,
(c) adjusting the temperature of the reactor system to a second reactor temperature setpoint and adjusting the pressure of the reactor system to a second reactor pressure setpoint that is greater than or equal to the first reactor pressure setpoint, after detection of initiation of the exothermic oligomerization reaction,
wherein the second reactor temperature setpoint and second reactor pressure setpoint are selected in combination to:
(i) ensure that the reaction mixture is molten,
(ii) ensure that the temperature of the reaction mixture is below the boiling point of the phenolic byproduct at the second reactor pressure setpoint, and
(iii) maintain the oligomerization reaction in the reaction mixture,
(d) maintaining the reactor system at the second reactor temperature setpoint and the second reactor pressure setpoint for a sufficient period of time to allow the reaction mixture to react to form an oligomer mixture,
(e) introducing the oligomer mixture to a polymerization reactor system operating under melt polymerization conditions sufficient to polymerize the oligomer mixture to a Mw of at least 9,000 g/mol (PC) and to remove the phenolic byproduct from the oligomer mixture,
thereby forming polycarbonate.
2. The method of claim 1 , wherein during step (b) the reaction mixture is monitored to detect initiation of the exothermic oligomerization reaction by monitoring the temperature of the reaction mixture to detect an exotherm indicating the initiation of the oligomerization reaction, by monitoring the concentration of phenolic byproduct in the reaction mixture to detect the initiation of the oligomerization reaction, or a combination thereof.
3. The method of claim 1 , wherein the diacid compound comprises an aliphatic diacid compound.
4. The method of claim 3 , wherein the aliphatic dihydroxy compound comprises isosorbide and the aliphatic diacid compound DDDA, C 36 hydrogenated dimer diacid, or both DDDA and C 36 hydrogenated dimer diacid.
5. The method of claim 1 , wherein the diaryl carbonate is an activated diaryl carbonate.
6. The method of claim 5 , wherein the activated diaryl carbonate is bismethylsalicylcarbonate.
7. The method of claim 1 , wherein the reaction mixture further comprises an aromatic dihydroxy compound selected from the group consisting of: BPA, hydroquinone, resorcinol, methylhydroquinone, methylresorcinol, DMBPC, and PPPBP.
8. The method of claim 1 , wherein the first reaction pressure is below atmospheric pressure and wherein the second reaction pressure is at or above atmospheric pressure.
9. The method of claim 1 , wherein the first reactor temperature setpoint is between 150° C. and 230° C. and wherein the second reactor temperature setpoint is between 80° C. and 150° C.
10. The method of claim 1 , wherein the reaction mixture is maintained in step (d) at a temperature within 15° C. of the temperature of the molten reaction mixture in step (b).
11. The method of claim 1 , wherein steps (a), (b), (c), and (d) occur in a stirred tank reactor and step (e) occurs in a plug flow reactor, a reactive extruder, or both a plug flow reactor and reactive extruder.
12. The method of claim 1 , wherein steps (a), (b), (c), (d), and (e) occur in a stirred tank reactor.
13. The method of claim 1 , wherein step (c) occurs 15 minutes or less after detection of initiation of the exothermic oligomerization reaction.
14. The method of claim 13 , wherein step (c) occurs 5 minutes or less after detection of initiation of the exothermic oligomerization reaction.
15. A method of forming polycarbonate comprising the steps of:
(a) introducing to a reactor system a reaction mixture comprising an activated diaryl carbonate, a transesterification catalyst, an aliphatic dihydroxy compound, and an aliphatic diacid compound,
(b) adjusting the temperature of the reactor system to a first reactor temperature setpoint and adjusting the pressure of the reactor system to a first reactor pressure setpoint between 0.7 bar and 1.2 bar, wherein the first reactor temperature setpoint is selected such that:
(i) it is sufficiently high to provide a molten reaction mixture,
(ii) it is sufficiently high to initiate an exothermic oligomerization reaction in the reaction mixture to form a polycarbonate oligomer and a phenolic byproduct, and
(iii) it is below the boiling point of the phenolic byproduct at the first reactor pressure,
wherein during step (b) the reaction mixture is monitored to detect initiation of the exothermic oligomerization reaction,
(c) adjusting the temperature of the reactor system to a second reactor temperature setpoint and adjusting the pressure of the reactor system to a second reactor pressure setpoint that is greater than or equal to the first reactor pressure setpoint, after detection of initiation of the exothermic oligomerization reaction,
wherein the second reactor temperature setpoint and second reactor pressure setpoint are selected in combination to:
(i) ensure that the reaction mixture is molten,
(ii) ensure that the temperature of the reaction mixture is below the boiling point of the phenolic byproduct at the second reactor pressure setpoint, and
(iii) maintain the oligomerization reaction in the reaction mixture,
(d) maintaining the reactor system at the second reactor temperature setpoint and the second reactor pressure setpoint for a sufficient period of time to allow the reaction mixture to react to form an oligomer mixture,
(e) introducing the oligomer mixture to a polymerization reactor system operating under melt polymerization conditions sufficient to polymerize the oligomer mixture to a Mw of at least 9,000 g/mol and to remove the phenolic byproduct from the oligomer mixture,
thereby forming polycarbonate.
16. The method of claim 15 , wherein during step (b) the reaction mixture is monitored to detect initiation of the exothermic oligomerization reaction by monitoring the temperature of the reaction mixture to detect an exotherm indicating the initiation of the oligomerization reaction, by monitoring the concentration of phenolic byproduct in the reaction mixture to detect the initiation of the oligomerization reaction, or a combination thereof.
17. The method of claim 15 , wherein the aliphatic dihydroxy compound comprises isosorbide the aliphatic diacid compound DDDA, C 36 hydrogenated dimer diacid, or both DDDA and C 36 hydrogenated dimer diacid and the activated diaryl carbonate comprises bismethylsalicylcarbonate.
18. The method of claim 1 , wherein the reaction mixture further comprises an aromatic dihydroxy compound selected from the group consisting of: BPA, hydroquinone, resorcinol, methylhydroquinone, methylresorcinol, DMBPC, and PPPBP.
19. The method of claim 15 , wherein the first reaction pressure is below atmospheric pressure and wherein the second reaction pressure is at or above atmospheric pressure.
20. The method of claim 15 , wherein the first reaction temperature setpoint is between 150° C. and 230° C. and wherein the second reaction temperature setpoint is between 80° C. and 150° C.
21. The method of claim 15 , wherein the reaction mixture is maintained in step (d) at a temperature within 15° C. of the temperature of the molten reaction mixture in step (b).
22. The method of claim 15 , wherein steps (a), (b), (c), and (d) occur in a stirred tank reactor and step (e) occurs in a plug flow reactor, a reactive extruder, or both a plug flow reactor and reactive extruder.
23. The method of claim 15 , wherein steps (a), (b), (c), (d), and (e) occur in a stirred tank reactor.
24. The method of claim 15 , wherein step (c) occurs 15 minutes or less after detection of initiation of the exothermic oligomerization reaction.
25. The method of claim 24 , wherein step (c) occurs 5 minutes or less after detection of initiation of the exothermic oligomerization reaction.