Vinyl chloride polymerization in microdroplet reactor - Les thèses en ...

IV.B. RESULTS AND DISCUSSION........................................................................................................... 75
IV.B.1) Pressure drop in the 180 µm ID capillary tube......................................................................... 78
IV.B.2) Pressure drop in the 250 µm ID capillary tube......................................................................... 80
V. FLOW CARTOGRAPHY IN MICROCHANNEL.................................................................................... 82
V.A. THE 180 µM CAPILLARY CIRCUIT .................................................................................................. 82
V.B. THE 250 µM CAPILLARY CIRCUIT .................................................................................................. 89
VI. DROPLET LENGTH MODELLING .................................................................................................... 92
VI.A. SHORT LITERATURE REVIEW ....................................................................................................... 92
VI.B. RESULTS AND DISCUSSION........................................................................................................... 94
VII. DROPLET SHAPE REPRESENTATION ............................................................................................ 96
VIII. PHENOMENA ENCOUNTERED IN MICROCHANNEL .................................................................... 98
IX. CONCLUSION ON THE HYDRODYNAMIC STUDY............................................................................ 99
CHAPTER III: ON-LINE KINETIC MONITORING OF S-PVC .............................................. 101
I. POLYMERIZATION IN MICROCHANNEL ......................................................................................... 103
I.A. POLYMERIZATION WITH LAUROYLE PEROXIDE AS INITIATOR IN THE AQUEOUS PHASE.............. 104
I.B. POLYMERIZATION WITH DI(4-TERT-BUTYLCYCLOHEXYL) PEROXYDICARBONATE AS INITIATOR IN
THE AQUEOUS PHASE........................................................................................................................... 105
I.C. POLYMERIZATION WITH DI(4-TERT-BUTYLCYCLOHEXYL) PEROXYDICARBONATE PRE-DISPERSED
IN THE VCM PHASE ............................................................................................................................. 106
I.D. VOLUME MEASUREMENT.............................................................................................................. 111
II. CHOICE OF THE APPROPRIATE ANALYTICAL TECHNIQUE FOR THE MONITORING OF VINYL
CHLORIDE POLYMERIZATION REACTION ......................................................................................... 114
II.A. THE CONTEXT.............................................................................................................................. 114
II.B. THE CLASSICAL TECHNIQUES FOR ON-LINE/IN-LINE ANALYSIS .................................................. 115
II.B.1) Ultrasound monitoring............................................................................................................. 115
II.B.2) Near Infrared (NIR) Spectroscopy........................................................................................... 115
II.B.3) Raman spectroscopy ................................................................................................................ 117
II.B.4) Choice of the on-line technique............................................................................................... 118
III. SECOND GENERATION MICROREACTOR FOR THE KINETIC STUDY OF THE VINYL CHLORIDE
POLYMERIZATION REACTION............................................................................................................ 119
III.A. REQUIREMENTS TO COMPLY...................................................................................................... 119
III.B. DIAGRAM OF THE EXPERIMENTAL SET-UP ................................................................................. 119
III.B.1) Experimental protocol ............................................................................................................ 122
III.B.2) The Raman experimental device ............................................................................................ 123
III.C. RAMAN SPECTROSCOPY – WORKING PRINCIPLE ........................................................................ 124
III.D. VISUALIZATION OF THE FIRST RESULTS OBTAINED WITH THE SECOND GENERATION
MICROREACTOR SET-UP....................................................................................................................... 124
IV. DEVELOPMENT OF THE MONITORING METHOD......................................................................... 125
IV.A. GLOBAL APPROACH................................................................................................................... 125
IV.B. SPECTRA OF PURE COMPONENTS ............................................................................................... 127
IV.C. REACTION SPECTRA DURING MONITORING................................................................................ 129
IV.D. DATA TREATMENT METHOD ...................................................................................................... 131
V. POLYMERIZATION KINETICS RESULTS ........................................................................................ 132
V.A. KINETIC MODEL AT CONSTANT VOLUME .................................................................................... 133
V.A.1) Kinetic model at variable volume ........................................................................................... 136
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