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Thermoplastic Elastomers with Complex Macromolecular Architectures

Thermoplastic Elastomers with Complex Macromolecular Architectures . 179 Technical Meeting, April 18-20,2011, Akron, OH. Nikos Hadjichristidis , University of Athens, Greece. Acknowledgements Professor Jimmy Mays, University of Tennessee at Knoxville, USA

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Thermoplastic Elastomers with Complex Macromolecular Architectures

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  1. Thermoplastic Elastomers with Complex Macromolecular Architectures 179 Technical Meeting, April 18-20,2011, Akron, OH Nikos Hadjichristidis, University of Athens, Greece

  2. Acknowledgements • Professor Jimmy Mays, University of Tennessee at Knoxville, USA • Assoc. Professor Sam Gido, UMASS Amherst, USA • Professor Roland Weidisch, Martin-Luther University at Halle, Germany • Assoc. Professor ErmisIatrou, University of Athens, Greece • Assoc. professor MarinosPitsikalis ,University of Athens, Greece • Dr George Koutalas, University of Athens, Greece • Dr Gabriel Velis, University of Athens, Greece • Many Thanks to the Rubber Division of ACS • Special Thanks to Professor Roderic Quirk

  3. STRENTH OF ANIONIC POLYMERIZATION • No Termination (Trully Living) • Well-Defined polymers(Low Molecular, Structural, Compositional Dispersity, Control of MW up to a Few Hundred Thousands) • Compatible with Dienes (Butadiene, Isoprene,2-Methyl-pentadiene) • Control of Microstructure (1,2; 1,4; cis and trans, Polyolefins by H2) • Not a Method of Choice in Industry. • Many Steps under inert and Clean Atmosphere, Time Consuming • Only if it is Necessary, e.g. KRATONS Why is Important for Industrial Application? Model Polymers, Structure-Properties relationships

  4. Synthesis and Properties of Well-Defined Non-Linear Homo(rheology) and Block Copolymers (morphology and micellization) Multiarm Stars MMP Dendritic Polymers wdLDPE Dumbell Dendritic BC Monomers: St, Bd, Is, 2VP, MMA, HIC, D3, NCAs PBocLL-PBLG-PBocLL Prog. Polym. Sci.,24, 875 (1999); Chem. Rev., 101, 3747 (2001) Prog. Polym. Sci.,30, 725 (2005); Adv. Polym. Sci., 189, 1 (2005), Chem. Rev., 109, 5528 (2009)

  5. Dendritic G2 (or Star),G3 Combs Dendritic Polymers G2, G3 Stars wd-PE (Models) α,ω-Branched r-Combs wd-LDPE (Models) wd-LDPE (Models) LDPE: Tree-like. High MW and Structural Dispersity Exact Combs MODEL POLYETHYLENES (Complex MA) Low MW and Structural Dispersity Understand the Behavior and Improve the Performance

  6. Block-Graft Copolymers Block-Comb Copolymers

  7. Block-Double-Graft Co- and Terpolymers Macromolecules, 29, 7022 (1996); 31, 5690 (1998); 31, 6697 (1998); 31, 7659 (1998); 33, 2039 (2000); 34, 6333 (2001); 35, 5903 (2002); 41, 4565 (2008); 42, 4155 (2009) Eur. Polym. J., 44, 3790 (2008); 45, 2902 (2009) Macromol. Symp., 215, 111 (2004); 233, 42 (2006) Polymer, 50, 6297 (2009)

  8. Synthesis ofBlock-Double-Graft Co- and Terpolymers

  9. Monitoring the synthesis of the BDG polymers by SEC

  10. Molecular Characteristics of Block-Double-Graft Terpolymers BDG6, BDG7, HDG BDG1 to BDG4 BDG5

  11. Morphological Characteristics of Block-Double-Graft Terpolymers BDG1 to BDG4 BDG6, BDG7, HDG BDG5

  12. BDG1 similar to BDG3 1st Group TEM SAXS χN (BDG1-BDG3): 1.1-0.53); BDG4: 0.27 PBd-1,4/PBd-1,2: One Phase BDG1 to BDG4

  13. 2nd Group SAXS Totally disorder state χN ~ 3 Asymmetric : 11 vol % PBd-1,2 BDG5

  14. 3rd Group TEM BDG7 similar SAXS Symmetric: ~ 50 vol % (total PDs) BDG6, BDG7, HDG

  15. Stress-strain curves for (1) BDG6, 9 junction points, branch mol.weight 14 000 g/mol; (2) BDG7, 3 junction points, branch molecular weight32 800 g/mol; (3) HDG, 9 junction points, branch molecular weight 12 500 g/mol; (4) Kraton D1101; and (5) PI-g-PS2 multigraft copolymer with 9 junction points, branch molecular weight13 000 g/mol. BDG6, BDG7, HDG

  16. PS-PIIx-PS PSS5-PIIx-PSS5 PS-PISIx-PS Block-Comb/Graft Copolymers Macromolecules, 38, 4996 (2005); 40, 5835 (2007); J. Polym. Sci., Polym. Chem., 43, 4030 (2005); 43, 4040 (2005) KGK-KautschukGummiKunststoffe, 61, 597 (2008)

  17. Synthesis ofPS-PIIx-PS Copolymers

  18. Monitoring the Synthesis of PS-PII10-PS by SEC PI macromonomer PI branch PS block PS-PII5copolymer PS-b-(PI-g-PI)-b-PS Fract. PS-b-(PI-g-PI)-b-PS

  19. Molecular Characteristics of thePS-PIIx-PS Copolymers a: SEC-TALLS inTHFat 35οC; b: SEC inTHF at 35οC; c: Membrane Osmometry in toluene at 40οC; d: Calculated fromMw and Mn, e: 1H NMR inCDCl3 at 30οC

  20. Synthesis ofPSS5-PIIx-PSS5 Copolymers

  21. Monitoring the Synthesis of PSS5-PII10-PSS5 PS branch PS macromon. PSS block (PS-g-PS)-b-(PI-b-PI) PI branch PI macromon. Fraction. PSS5-PII10-PSS5 (PS-g-PS)-b-(PI-b-PI)-b-(PS-g-PS)

  22. Molecular Characteristics ofPSS5-PIIx-PSS5 Copolymers a: SEC-TALLS inTHFat 35οC; b: SEC inTHF at 35οC; c: Membrane Osmometry in toluene at 40οC; d: Calculated from Mw and Mn; e: 1H NMR inCDCl3at 30οC

  23. Synthesis of PS-PISIx-PS Copolymers

  24. Monitoring the Synthesis of PS-PISI4-PS by SEC PS-b-PI arm PS-b-PI macromon. PS arm block PS block of the bb PS-b-[PI-g-(PI-b-PS)]-b-PS PS-b-[PI-g-(PI-b-PS)] PS-b-[PI-g-(PI-b-PS)]-b-PS Fractionated

  25. Molecular CharacteristicsPS-PISIx-PS Copolymers a: SEC-TALLS inTHFat 35οC; b: SEC inTHF at 35οC; c: Membrane Osmometry in toluene at 40οC; d: Calculated fromMw and Mn;e: 1H NMR inCDCl3at 30οC

  26. ΤΕΜ Results χSI= 0.074 at 120οC ρPS= 1.05 g/cm3 at 120οC ρPI= 0.91 g/cm3 at 120οC

  27. PSS5-PII5 (φPS= 0.18) PSS5-PII10-PSS5 (φPS= 0.18)

  28. Stress-Strain Behavior of Block-Comb/Graft Copolymers Influence of the Architecture Kraton D1101

  29. Conclusions • Anionic Polymerization High Vacuum Techniques Lead to Well-Defined Thermoplastic Elastomers with Complex Macromolecular Architectures • These Novel Thermoplastic Elastomers Show Interesting Mechanical Properties • Strain at Break Can Greatly Exceed Those of Commercial TPE

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