Polymer Synthesis, Characterization and Processing

1. Polymer Synthesis, Characterization and Processing R. A. Weiss, M. Cakmak, S. Gupta, E. McClanahan University of Akron Annual Review, October 28, 2011

2. Topics Under Investigation • Characterization of PP-OH from Mike Chung • Synthesis of High Temperature Polymers • Characterization and Processing of PP from Borealis

3. Characterization of PP-OH from M. Chung Need access to high temperature GPC (Brian Coughlin, UMass (Amherst))

4. Intensity (a.u.) 10 15 20 25 30 35 40 45 50 2θ (deg) Effect of OH-substitution on Crystal Structure Wide-Angle X-Ray Diffraction PP and PP-OH have monoclinic crystal structures – no effect of OH substitution

5. Lamellar Thickness of Crystals Small Angle X-Ray Scattering) Polypropylene d = 15.0 nm PP-OH (3.93% OH) d = 12.3 nm Iq2 (a.u.) PP-1 PP-2 PP-OH (1.3) PP-OH (1.4) PP-OH (1.7) PP-OH (3.9) 0 0.25 0.5 0.75 1.0 1.25 1.5 1.75 2.0 q (nm-1) Spherulite (space-filling) Growth Direction d Chain Direction lamella thickness (long spacing) Scattering Invariant

6. Melt Rheology (Dynamic Experiments) aTw (1/s) aTw (1/s) • TTS works well • With increasing [OH], the melt viscosity increases and the melt becomes more elastic

7. Melt Rheology of PP-OH Samples 105 104 103 102 101 100 τ ~ 0.01 s τ ~ 0.3 s PP (Mv = 511 kg/mol) G” η’0.1 ~ 103 Pa.s G’ 106 105 104 103 102 bTG’ or bTG” (Pa) PP-OH (1.7 mol% OH) (Mv = 388 kg/mol) ?? 2 2 G” 1 1 G’ η’0.1 ~ 2 x 104 Pa.s 10-2 10-1 100 101 102 103 aTω (s-1) ViscoelasticMastercurves @ 200C

8. Cole-Cole Plot

9. Anomalous Behavior for PP-OH (3.9 mol% OH) Weak Elastic Network No viscous flow bTG’ or bTG” (Pa) 2 G0.1 ~ 2 x 103 Pa 1 η’0.1 ~ 2 x 104 Pas aTω (s-1)

10. Steady Shear Viscosity h (Pa.s)

11. Sulfonated Poly(ether ether ketone) Red: acid Blue Zn-salt Tm %xyl % Crystallinity Tg

14. Borealis Polypropylene Material Commercial Grades

15. PP Rheology