1. 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

2. Barium HT-PBd

3. 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

4. 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

5. 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

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

7. trans-SBR: Light Tires50 70 90
110
130
150
170
190
210 95
100
105
115
120
125
Tear Resistance
Trans-SBR
Rolling Resistance
better
Current Technology

8. 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

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

10. 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

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

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

13. trans Content vs. Styrene

14. Ethyl Benzoate Coupled trans-SBR10 20 30 40 50 60 70 80 90 1 2 3
Base Mooney
Coupled Mooney
1.00 mmol
2.00 mmol
3.00 mmol

15. SiCl4 Coupled trans-SBR10 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

16. Styrene Sequence by Ozonolysis

17. Styrene Sequence (New Catalyst) via ozonolysis

18. Tensile Stress Growth: HTSBR @ 0.1s-1

19. HTSBR Elastic Moduli

20. HTSBR Tan Delta

21. 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

22. 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

23. 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

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

25. 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