Cobalt HT-PBd Rev Heat Flow (W/g) Heat Flow (W/g) -72.33°C(I) 0.1229J/g/°C -74.58°C -67.55°C -35.28°C 46.94°C 38.36°C 33.80°C 26.17J/g -71.06°C(I) 0.1288J/g/°C -76.45°C -69.39°C -37.56°C 62.27°C 38.28°C 33.38°C 46.67J/g 55.75°C 29.32°C 63.58°C 38.12°C 33.34°C 16.81J/g 56.40°C 0.075 0.175 0.275 Nonrev Heat Flow (W/g) -0.25 0.00 Rev Heat Flow (W/g) -0.50 Heat Flow (W/g) -125 -75 -25 25 75 Temperature (°C) Exo Up Universal V2.5H TA Instruments

Barium HT-PBd

Melting vs. trans Content trans Content (wt %) 60 65 70 75 80 85 90 95 100 -40 -20 20 40 120 140 160 Tm (°C) K Co Ba

trans - PBd Observations Tg decreases with increased cis content Tm increases as trans content increases trans content decreases with increasing MW trans content < 80%: a single melting endotherm trans content > 86%: two endotherms on heating

New Ba trans-PBD Extremely low vinyl content Tg = -90 to -95°C typically less than 5% Tg = -90 to -95°C Tm = 10 to 40°C controlled by reaction temperature catalyst ratio catalyst modifier

HTPBd via Alkylated Ba/TOA 90% conversion in 1 hr.

trans-SBR: Light Tires 50 70 90 110 130 150 170 190 210 95 100 105 115 120 125 Tear Resistance Trans-SBR Rolling Resistance better Current Technology

trans-SBR Can control Tg and Tm through styrene content Above 22% styrene crystallinity disappears High tear resistant polymer with low heat build-up Lug tear in RLT, RMT Chip/chunk in farm, OTR Tread wear/RR in RLT Light tire ply

HTSBR via Alkylated Ba/TOA Bd: ~90% conversion in 1 hr.

Conversion PBD vs. SBR Monomers, both Bd and Styrene, alone = quick reaction Styrene actually reacts more quickly than Bd Combining Styrene and Butadiene slows the styrene rate considerably - Bd unaffected Temperature has a large effect on overall trans content lower temperature = higher trans

HTSBR in-situ Catalyst: 1/4/3 BaDMAEE/TOA/n-BuLi 90°C

HTSBR n-BuLi reduced Catalyst: 1/4/3 BaDEGEE/TOA/n-BuLi 90°C

trans Content vs. Styrene

Ethyl Benzoate Coupled trans-SBR 10 20 30 40 50 60 70 80 90 1 2 3 Base Mooney Coupled Mooney 1.00 mmol 2.00 mmol 3.00 mmol

SiCl4 Coupled trans-SBR 10 20 30 40 50 60 70 1 2 3 Base Mooney Coupled Mooney 1.00 mmol SiCl4 1.50 mmol SiCl4 2.00 mmol SiCl4

Styrene Sequence by Ozonolysis

Styrene Sequence (New Catalyst) via ozonolysis

Tensile Stress Growth: HTSBR @ 0.1s-1

HTSBR Elastic Moduli

HTSBR Tan Delta

n-BuLi Initiator Review RLi (alone) - an initiator for anioninc polymerization PBd microstructure: 55% trans, 35% cis, and 10% 1,2 structure results This gives no melt or strain induced crystallization SBR - block styrene results (not a random distribution) styrene reacts much slower than Bd

n-BuLi, Al & Ba Complexes The following are NOT anionic initiators for diene or vinyl aromatic polymerizations R3Al (RO)2Ba Reduced n-BuLi RLi + R3Al  [R4Al]-Li+ Alkylated Ba(OR)2 R3Al + Ba(OR)2  BaR2•AlR3 ate complexes

High trans Catalyst Possible Mechanism The addition of RLi to BaR2•AlR3 creates an initiator for diene and vinyl aromatic polymerization Possible Mechanism BaR2•AlR3 + RLi  [BaR3]-Li+•AlR3 Barium/n-BuLi ate complex is the potential initiator for polymerizations

Mechanism A) B) trans - 1,4 cis - 1,4 syn anti butadiene vinyl Ba H OR

Acknowledgements Special thanks to The Goodyear Tire & Rubber Co. for permission Goodyear Exploratory Polymer Research Bill Hsu Jinping Zhou Laurie Austin Chad Jasiunas Corey Yon Steven Gray Aaron Ryba Ronald Kovalak Also thanking for their hard work and dedication: Kristine Ludwig Martin Sentmanat Abderrahim Khadir