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Ohjo University Library @ 1987 The Kinetics of a Methyl Hethacrylate Polymerization Initiated by the Stable Free Radicals in Irradiated Polytetrafluoroethylene and Properties of the Resultant Graft Polymer A Dissertation Presented to The Faculty of the College of Engineering and Technology Ohio University In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Karen Ann Ehnot Donato --. June, 1987 OHJO UNIVERSITY LIBRARY @ 1987 Karen Ann Ehnot Donato All Rights Reserved This dissertation has been approved by the Department of Chemical Engineering and the College of Engineering and Technology of Ohio University Associate Professor of Chemical Engineering Dean of the College of Engineering and Technology TABLE OF CONTENTS Page List of Figures vi List of Tables XV List of Appendices xvi ii Acknowledgment ixx I. Introduction 1 11. Polytetrafluoroethylene 3 11.1 Structure and Properties of PTFE 3 11.2 Effects of Radiation on Polytetrafluoroethylene 11.3 Melt Extrudable Fluorocarbon Resins 11.4 Radiation Induced Grafting of PTFE Films with Vinyl Monomers 111. Free Radical Chain Polymerization 111.1 Theory of Free Radical Polymerization 111.2 Inhibition in Free Radical Polymerization 111.3 Hethyl nethacrylate Homopolymerization 111.4 Gel(Trommsdorf) Effect IV. Kinetics node1 for Irradiated PTFE Initiated HM Polymerization IV. 1 Kinetics Model from Earlier Work(69) V. Experimental Procedure for Production of the PTFE-PW Graft Polymer V. 1 Test Tube Runs V. 2 Factorial Design and Reaction Conditions for the Scaled-up Reaction V. 3 Kinetics Runs in Bulk VI. Results of the Graft Polymerization VI.l Test Tube Factorial VI. 2 Bulk Factorial VI. 3 Kinetics Data in Test Tubes(68) VI.4 Kinetics Runs in Bulk VI. 5 Temperature Excursions During Scaled-up Reactions VI. 6 Power Levels for Agitation VII. Discussion of Kinetics Results VII.l Test Tube Factorials VII. 2 Scaled-up Factorial VII. 3 Comparison of Test Tube and Bulk Factorials VII.4 The Mechanics of the Reaction VII. 5 Undesirable Side Reactions VII.6 Determination of Ro VII. 7 Solution of the Conversion Equations VII. 8 Solution of Conversion Equation for Test Tube Runs VII.9 Bulk Reactor Data VII.10 Prediction of Conversion in the Factorial Runs from the Rate Constants in the Kinetics Runs VII.ll Estimation of the Number of PKM Repeat Units per Chain VII.12 Temperature Excursions VII.13 Agitation Excursions VIII. Background for Polymer Characterization VIII.l Rheology VIII.1.a Melt Flow Behavior VIII.1.b Rheology and its Governing Equations VIII.1.c Flow Instabilities VIII.1.d Die Swell VIII.2 Temperature Transitions VIII.2.a Glass Transition Temperature VIII.2.b Melting Temperature VIII.2.c Determination of Glass Transition and Melting Temperatures VIII.3 Resistance of Polymers to Chemical Attack VIII.4 Mechanical Properties of Polymers VIII.4.a Elastic Modulus VIII.4.b Dynamic Mechanical Analysis VIII.4.c Mechanical Properties and Transition Temperatures IX. Equipment used for Product Characterization IX. 1 Melt Rheology 1X.l.a Instron Melt Rheometer 1X.l.b Kayeness Melt Rheometer IX. 2 Temperature Transitions IX. 3 Chemical Resistance IX. 4 Dynamic Mechanical Testing X. Results of Product Characterization 128 X. 1 Melt Rheology 128 X.1.a Instron Melt Rheometer 128 X.1.b Kayeness Melt Rheometer 128 X. 2 Differential Scanning Calorimetry 154 X. 3 Chemical Resistance 175 X. 4 Dynamic Mechanical Analysis 177 XI. Discussion and Interpretation of Product Characterization 185 XI.l Melt Plow Behavior 185 XI.1.a Instron Melt Rheometer 185 XI.1.b Melt Rheology on the Kayeness Rheometer 186 XI. 2 Differential Scanning Calorimetry 201 XI. 3 Chemical Resistance 203 XI.4 Dynamic Mechanical Analysis 205 XII. Applications 210 XIII. Summary 212 XIII.l Conclusions 212 XIII.2 Recommendations 215 v XIV. Appendices 217 XV. Bibliography 243 XVI. Abstract following page 249 List of Finvres Page Figure 1: Melt viscosity of irradiated PTFE as a function of dose(l5). 7 Figure 2: Degree of grafting-time curves at various preirradiation doses (Mrad) using acrylic acid and PTFE films. Doses(Mrad): (0) 1; (0) 3; (A) 5; 6)10. Grafting Conditions: AAc conc, 40 wt %; grafting temperature, 308K(35OC); film thickness, 80 m(40). Figure 3: Degree of grafting-time curves at various acrylic acid concentrations using PTFE films: preirradiation dose, 5 Mrad; grafting temperature, 308K(35OC); film thickness, 80ym(40). Figure 4: Degree of grafting-time curves at various grafting temperatures(K(OC)) using acrylic acid PTFE films. Temperatures: (0) 288(15); (0)298(25); (A) 308(35); (0) 318(45); (0) 333(60). Grafting conditions, except preirradiation dose (5 Mrad), are the same as in Figure 2(40). Figure 5: Degree of grafting-time curves at various PTFE film thicknesses (~m)using acrylic acid. (A) 80; (0) 130; (o) 190. Grafting conditions, except preirradiation dose (5 Wad), are the same as in Figure 2(40). Figure 6: The change of mechanical properties of the irradiated PTFE films grafted with acrylic acid on wetting in distilled water as a function of degree of grafting. Grafting conditions: acrylic acid concentration, 40 wt X; grafting temperature, 308K(35OC); film thickness, 804m(38). Figure 7: Equipment used for scaled up reactions. Figure 8: Log-probability plot of particle size distribution of DLX-6000 as received. List of Figures (Cont.) Figure 9a: ESR scan of DLX-6000 as 5eceived. Conditions: G = 2.0 X 10 ; scan time = 4 minutes! Mod = 2G. For DPPH, G = 2.5 X 10 , Mod = 1G. Figure 9b: ESR scan of particles with a diameter greater than 150 microns in DLX-6000. Conditions are the same as in Figure 9a. DPPH and PTFE curves are slightly displaced compared to Figure 9a. Figure 9c: ESR scan of particles with a diameter less than 150 microns in DLX-6000. Conditions are the same as in Figure 9a. Figure 10a: Conversion to graft versus time at 333K(60°C) in test tubes with Fluone L-169 in a 1:3 ratio with HMA. The predicted curve from Equation IV.1.9 is shown. Figure lob: Degree of Grafting versus time at 333K(60°C) in test tubes with Fluone L-169 in a 1:3 ratio with MU. The predicted curve from Equation IV.l.ll is shown. Figure lla: Conversion versus time at 353K(80°C) in test tubes with 1 gram Fluone L-169 to 3 milliliters IMA. The predicted relationship from Equation IV.1.9 is shown. Figure llb: Degree of Grafting versus time at 353K(80°C) in test tubes with 1 gram Fluone L-169 to 3 milliliters !MA. The predicted relationship from Equation IV.l.ll is shown. Figure 12a: Conversion to graft versus time at 343K(70°C) in test tubes with 2 grams of Polymiste F-5A to 5 milliliters H)IA. The predicted relationship from Equation IV.1.9 is shown. Figure 12b: Degree of Grafting versus time at 343K(70°C) in test tubes with 2 grams of PolymisteF-5A to 5 milliliters M. The predicted relationship from Equation IV.l.ll is shown. 54 List of Figures (Cont.) Figure 13a: Per cent conversion to graft versus time at 343K(70°C) in the bulk reactor. The predicted relationship from equation IV.1.9 is shown. Figure 13b: Degree of grafting versus time at 343K(70°C) in bulk reactor. The predicted relationship from equation IV.l.ll is shown. Figure 14a: Per cent conversion to graft versus time at 353K(80°C) in the bulk reactor. The predicted relationship from equation IV.1.9 is shown. Figure 14b: Degree of grafting versus time at 353K(80°C) in bulk reactor. The predicted relationship from equation IV.l.ll is shown. Figure 15: Total conversion from scaled-up reactor for one hour reaction times as a function of temperature. Figure 16: Conversion to graft from scaled-up reactor for one hour reaction times as a function of temperature. Figure 17: Conversion to homopolymer from scaled-up reactor for one hour reaction times as a function of temperature. Figure 18: Degree of Grafting for scaled-up reactor for one hour reaction times as a function of temperature. Figure 19: Reactor temperature as a function of time for a bulk reaction at 333K(60°C) for one hour. Figure 20a: Reactor temperature as a function of time for bulk reactions at 343K(70°C) for one hour. Figure 20b: Power level as a function of time for bulk a reaction at 343K(70°C) for one hour. Figure 21a: Reactor temperature as a function of time for bulk a reaction at 353K(80°C) for three hours. List of Figures (Cont.) Figure 21b: Power level as a function of time for a bulk reaction at 353K(80°C) for three hours. Figure 22: ESR scan of LX 6000. For PTFE: G = 2.0 X 109. Mod- = 2.06. For DPPH: G = 2.5 X 10'; Mod = 1.06. Figure 23: ESR scan of Polymist" F5A. Curve 1 is at the same conditions use9 in Figure 22. Curve 2 is at G = 4.0 X 10 . Figure 24: ESR scan of ljluona L-169. For PTFE: G = 2.0 X 10 Mod = 2.06. For DPPH: G = 2.5 X loo: Mod = 1.W. Figure 25: Parity plot of conversion values predicted from equation VII.7.1 versus experimental values for reactions in test tubes at 333K(60°C) using Fluon* L-169 in a ratio of 1 gram PTFE to 3 milliliters HHA. A line with a slope equal to 1 is shown. Figure 26: Parity plot of conversion values predicted from equation VII.7.1 versus experimental values for reactions in test tubes at 353K(80°C) using Fluon* L-169 in a ratio of 1 gram PTFE to 3 milliliters HHA.
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