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Intensification of NMP and ATRP (co)polymer syntheses by microreaction technologies

Prof. Christophe A. Serra Caine Rosenfeld, Florence Bally, Dambarudhar Parida, Dhiraj Garg. Intensification of NMP and ATRP (co)polymer syntheses by microreaction technologies. http://ics-cnrs.unistra.fr/caserra. Atelier de Prospective du GFP , Paris, Dec. 4 th , 2014. Outline. 1. Context

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Intensification of NMP and ATRP (co)polymer syntheses by microreaction technologies

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  1. Prof. Christophe A. Serra Caine Rosenfeld, Florence Bally, Dambarudhar Parida, Dhiraj Garg Intensification of NMP and ATRP (co)polymer syntheses by microreaction technologies http://ics-cnrs.unistra.fr/caserra Atelier de Prospective du GFP, Paris, Dec. 4th, 2014

  2. Outline • 1. Context • 2. Microprocessoverview • 3. Results • Synthesis of linear, block and branched (co)polymers • Influence of micromixing • Influence of microreactorgeometry • Influence of pressure • CFD Analysis • 4. Conclusion

  3. Outline • 1. Context • 2. Microprocessoverview • 3. Results • Synthesis of linear, block and branched (co)polymers • Influence of micromixing • Influence of microreactorgeometry • Influence of pressure • CFD Analysis • 4. Conclusion

  4. 1. Context • Motivation • Synthesis of architecture-controlled (co)polymers • Block, linear or branched architectures • low PDI, defined MW • Applications in drug delivery, photoresist • Two-fold strategy • Chemistry • Rely on controlled/”Living” polymerization techniques • ATRP, NMP • Intrinsically “slow” reactions • Process • Development of an intensified and integrated continuous-flow microprocess

  5. Outline • 1. Context • 2. Microprocessoverview • 3. Results • Synthesis of linear, block and branched (co)polymers • Influence of micromixing • Influence of microreactorgeometry • Influence of pressure • CFD Analysis • 4. Conclusion

  6. 2. Overview • Polymerization microprocess Synthesis (CMS) Monomer A Solvent Pump Initiator µreactor 1 Copolymer µmixer µreactor 2 Monomer B Pump Rosenfeld et al., React. Eng., 1 (5) (2007) 547-552; Bally et al., React. Eng., 5 (11-12) (2011) 542–547

  7. 2. Overview • Polymerization microprocess Synthesis (CMS) Monomer A Solvent Pump Initiator µreactor 1 Copolymer µmixer µreactor 2 Monomer B Pump Analysis (COA) Solvent Eluate Injection GPC Column Dilution Waste of detectors Train Rosenfeld et al., React. Eng., 1 (5) (2007) 547-552; Bally et al., React. Eng., 5 (11-12) (2011) 542–547

  8. Recovery (IPR) 2. Overview • Polymerization microprocess Synthesis (CMS) Monomer A Solvent Pump Initiator nanoparticles solvent µreactor 1 µmixer µmixer Copolymer µmixer µreactor 2 Non solvent Monomer B Pump Analysis (COA) Solvent Eluate Injection GPC Column Dilution Waste of detectors Train Rosenfeld et al., React. Eng., 1 (5) (2007) 547-552; Bally et al., React. Eng., 5 (11-12) (2011) 542–547

  9. 2. Synthesis (CMS) • Continuous-microflow synthesis unit To COA

  10. 2. Synthesis (CMS) • Microreactors • Microtubular reactors (ID 876 µm) • Coiled tube (CT)

  11. 2. Synthesis (CMS) • Microreactors (cont’d) • Microtubular reactors (ID 876 µm) • Coiled tube (CT) • Coil flow inverter (CFI) • Better mixing • Lower RTD End of the helix After 1st bend Outlet After 2nd bend Inlet A.K. Saxena and K.D.P. Nigam, AIChE J., 1984, 30, 363-368

  12. 2. Microprocess features • Screening • Operating conditions • Flow rate, temperature, pressure, residence time, monomer concentration • Polymerization methods • FRP, CRP (NMP, ATRP, RAFT) • Rapid measurements • Analysis every 12 minutes • Libraries • Homopolymers • Copolymers

  13. 2. Microprocess features • Fully automated • Software controlled • Over night experiments • Pressure sensors • Temperature probes • Modular • New reaction blocks • New detectors • Raman • NIR • Inline polymer recovery • Colloidal suspension

  14. Outline • 1. Context • 2. Microprocessoverview • 3. Results • Synthesis of linear, block and branched (co)polymers • Influence of micromixing • Influence of microreactorgeometry • Influence of pressure • CFD Analysis • 4. Conclusion

  15. 3. Copolymers (CMS) • Continuous one-step statistical copolymerization • Atom Transfer Radical Polymerization (ATRP) • Librairies of poly(DMAEMA-BzMA) / Influence of micromixer

  16. 3. Copolymers (CMS) • Continuous one-step statistical copolymerization • Continuous-flow setup 75°C

  17. 3. Copolymers (CMS) • Continuous one-step statistical copolymerization (cont’d) • Micromixers Parida et al., Green. Proc. Synt., 6 (1) (2012) 525-532

  18. 3. Copolymers (CMS) • Continuous one-step statistical copolymerization (cont’d) +35% Parida et al., Green. Proc. Synt., 6 (1) (2012) 525-532

  19. 3. Copolymers (CMS) • Continuous one-step statistical copolymerization (cont’d) +6,000 -50% Parida et al., Green. Proc. Synt., 6 (1) (2012) 525-532

  20. 3. Copolymers (CMS) • Continuous one-step statistical copolymerization (cont’d) X100 Parida et al., Green. Proc. Synt., 6 (1) (2012) 525-532

  21. 3. Copolymers (CMS) • Continuous two-step block copolymerization PBA-b-PS • Nitroxide-Mediated Polymerization (NMP) • PBA-b-PS with low polydispersity index (PDI) • Mixing between viscous and liquid fluids by means of microstructured mixers

  22. Fluid B Fluid A Fluid B Fluid A Multilamination Multilamination 3. Copolymers (CMS) • Micromixers Fluid B Fluid A Mixing by … Bilamination ML20 ML50 CF ML45 Number of microchannels 1 16 15 10 Film thickness 450µm 45µm 20µm 50µm

  23. 3. Copolymers (CMS) • Sorting by form factor (F) • Multilamination • Bilamination

  24. Fluid B Fluid A Fluid B Fluid A Multilamination Multilamination 3. Copolymers (CMS) • Micromixers Fluid B Fluid A Mixing by … Bilamination ML20 ML50 CF ML45 Number of microchannels 1 16 15 10 Film thickness 450µm 45µm 20µm 50µm F 2.8 3.9 4.6 1

  25. 3. Copolymers (CMS) • Continuous two-step block copolymerization(cont’d) • 1st block - 3:1 vol. BA/Toluene - "High" [AX]0 - 5% mol. free TIPNO • 2 equiv. Acetic anhydride Not purified Rosenfeld et al., Chem. Eng. Sci., 62 (2007) 5245-5250.

  26. 3. Copolymers (CMS) • Continuous two-step block copolymerization (cont’d) • Copolymer Not purified BR ML50 ML20 CF Rosenfeld et al., Chem. Eng. J., 15 (S1) (2008) S242-S246

  27. 2 Q2=9.3 µL/min 1.8 I p 1.6 1.4 1.2 0.5 1.5 2.5 3.5 4.5 5.5 Re' 3. Copolymers (CMS) • Continuous two-step block copolymerization (cont’d) • Influence of the micromixer geometry • Most efficient micromixer tested: wider and fewer microchannels  Mainly controlled by the velocity CF ML45 PDI ML20 ML50 F Rosenfeld et al., Lab. Chip., 8 (2008) 1682-1687

  28. Outline • 1. Context • 2. Microprocessoverview • 3. Results • Synthesis of linear, block and branched (co)polymers • Influence of micromixing • Influence of microreactorgeometry • Influence of pressure • CFD Analysis • 4. Conclusion

  29. 3. Microreactor geometry (CMS) • Recall one-step statistical copolymerization in CT Viscosity • Microreactor with internal mixing to overcome diffusion limitations

  30. 3. Microreactor geometry (CMS) • Linear polymers • Atom Transfer Radical Polymerization (ATRP) • Librairies of poly(DMAEMA) / CT vs. CFI

  31. 3. Microreactor geometry (CMS) • Linear polymers (cont’d) ID= 876 µm CT, 3 m CFI, 3 m • No significant increase in conversion between CT and CFI Parida et al., Macromolecules, 47 (10) (2014) 3282–3287.

  32. 3. Microreactor geometry (CMS) • Linear polymers (cont’d) ID= 876 µm CT, 3 m CFI, 3 m • Mn is higher in case of CFI (avg. +2000 g/mol) • Significant reduction in PDI for CFI (-0.13) Parida et al., Macromolecules, 47 (10) (2014) 3282–3287.

  33. 3. Microreactor geometry (CMS) • RTD measurements CFI CT • RTD is narrower in CFI compared to CT • High Pe in case of both reactors indicates low axial dispersion Parida et al., Macromolecules, 47 (10) (2014) 3282–3287.

  34. 3. Microreactor geometry (CMS) m m m • Branched polymers • Self-Condensing vinyl coPolymerization, adapted to ATRP b I a m m Inimer = Monomer + Initiator m m* b m b a m m* m m* a m 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM) m* Matyjaszewskiet al., Macromolecules 1997, 30, 5192 a- b m

  35. 3. Microreactor geometry (CMS) • Branched polymers (cont’d)

  36. 3. Microreactor geometry (CMS) • Branched polymers (cont’d) • DMAEMA and BIEM conversions + 7.5% • Higher BIEM conversion for CFI Parida et al., Macromolecules, 47 (10) (2014) 3282–3287.

  37. 3. Microreactor geometry (CMS) • Branched polymers (cont’d) • GPC traces – Batch reactor • Presence of BIEM-initiated macromonomers/oligomers Parida et al., Macromolecules, 47 (10) (2014) 3282–3287.

  38. 3. Microreactor geometry (CMS) • Branched polymers (cont’d) • GPC traces (2 hrs) 10 % 5 % • Highest oligomeric units in batch • Lowest in CFI Parida et al., Macromolecules, 47 (10) (2014) 3282–3287.

  39. 3. Microreactor geometry (CMS) • Branched polymers (cont’d) • Polymer characteristics (BIEM 5mol% @ 2 hrs) +700 -0.28 • Mn exhibits the following trend: batch < CT < CFI • PDI follows the opposite trend: batch > CT > CFI Parida et al., Macromolecules, 47 (10) (20141)3282–3287

  40. 3. Microreactor geometry (CMS) • Branched polymers (cont’d) • Impact of flow inversion on molecular characteristics • Highest branching efficiency in CFI and lowest in batch • Controlled branched structure in microreactors especially in CFI Parida et al., Macromolecules, 47 (10) (20141)3282–3287

  41. Outline • 1. Context • 2. Microprocessoverview • 3. Results • Synthesis of linear, block and branched (co)polymers • Influence of micromixing • Influence of microreactorgeometry • Influence of pressure • Scale-up • CFD Analysis • 4. Conclusion

  42. 3. Operating parameters (CMS) • Effect of pressure • Chemical system

  43. 3. Pressure (CMS) • Effect of pressure • Procedure

  44. 3. Pressure (CMS) • Effect of pressure (cont’d) • Polymer characteristics • Decrease in activation volume • Reduced termination • Increased density, thus increased residence time Parida et al., J. Flow Chem., 4 (2) (2014) 92-96.

  45. 3. Pressure (CMS) • Effect of pressure (cont’d) • Microreactor dimension 576 µm 876 µm 1753 µm Parida et al., J. Flow Chem., 4 (2) (2014) 92-96.

  46. 3. Pressure (CMS) • Effect of pressure (cont’d) • Microreactor dimension • Reduced diffusion distance Parida et al., J. Flow Chem., 4 (2) (2014) 92-96.

  47. Outline • 1. Context • 2. Microprocessoverview • 3. Results • Synthesis of linear, block and branched (co)polymers • Influence of micromixing • Influence of microreactorgeometry • Influence of pressure • Scale-up • CFD Analysis • 4. Conclusion

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