1. This is a presentation on MVP
Preparation and Characterization of MVP Polymers
Bill Gross, Bill Hsu, and Adel Halasa*
The Goodyear Tire and Rubber Company
Akron, OH

2. MVP Polymer
Preparation of MVP via Anionic Polymerization employing three monomers Isoprene for traction styrene for strength and butadiene for wear the catalyst system is n-BuLi and the modifier is TMEDA

3. MVP Polymer
It is well known in the Rubber Industries that a tread rubber is a blend of two or three polymers in order to balance traction wear and RR( fuel saving) The major problem with this concept is the following. A. miscibility. B filler distribution& dispersion

4. MVP Polymer
In this approach we are attempting to micro-engineer the molecular chain to avoid all the problems of polymer blend and filler distribution. Anionic polymerization of S/I/B ter-polymer has met this criteria

5. Reactivity Ratio of MVP Polymer
The reactivity ratios of the three monomer employed in this system are dependant on the polar modifier TMEDA the r1 for Bd and r2styrene are enhanced while r3 for Isoprene is decreased thus microstructure which control the Tg is dependant of the modifier addition to the polymerization

6. MVP Polymer
In this system we used Batch polymerization methods to control the MVP molecular design via the addition of TMEDA during the reaction and taking samples for analysis

7. Symbolic MVP Polymer Chain
Modifier added
Low Tg
(Wear)
Phase
mixing
High Tg
(Traction)

8. Microengineering Polymer Chain by Polymer Synthesis
Using three monomers; styrene, isoprene, and butadiene
Using polar modifiers added during the polymerization
Controlling molecular weight by catalyst concentration
Controlling microstructure by polar to catalyst ratio
Coupling polymer chains to improve the processibility
Controlling Tg by styrene concentration
Controlling Tg by isoprene microstructure

9. Conversion vs Time for SIBR

10. DSC of MVP Polymer % Conversion Temperature (ºC) -79 ºC -40 ºC -80 ºC
-120
-100
-80
-60
-40
-20 20 40
-79 ºC
-80 ºC
-40 ºC
-20 ºC
-19 ºC
Temperature (ºC)
% Conversion
30 %
50 %
80 %
100 %

11. Microstructure of MVP/SIBR

12. Microstructure of MVP/SIBR

13. Tg of MVP Polymer

14. Theoretical Integral Polymer

15. Physical Properties of Polymer in CB
Tan δ -20
Tan δ 0
Tan δ 60
IBR
0.535
0.252
0.086
45/45/10
0.520
0.370
0.061
40/40/20
0.388
0.500
0.078
35/35/30
0.834
0.115
High Tan δ -20; Excellent wear, High Tan δ 0; Excellent traction, Low Tan δ 60; Excellent rolling resistance.

16. Blends (50/50 NR) Polymer Tan δ -20 Tan δ 0 Tan δ 60 IBR 0.299 0.145
0.075
45/45/10
0.492
0.165
0.062
40/40/20
0.550
0.285
35/35/30
0.089
0.419
0.098
High Tan δ -20; Excellent wear, Low Tan δ 0; Excellent traction, High Tan δ 60; Excellent rolling resistance.

17. Blends of MVP Polymer with 70/30 cis-PBD
Tan δ -20
(Wear)
Tan δ 0
(Traction)
Tan δ 60
(RR)
IBR
0.395
0.146
0.092
45/45/10
0.350
0.205
0.063
40/40/20
0.421
0.240
0.072
35/35/30
0.093
0.524
0.097
High Tan δ -20; Excellent wear, Low Tan δ 0; Excellent traction, High Tan δ 60; Excellent rolling resistance.

18. Tan Delta of MVP Polymer with Styrene Contents
Temperature (ºC)
-100
-80
-60
-40
-20 20 40 60
Log Tan δ -1 -2 -3
10 %
20 %
30 %

19. MVP/NR (50/50) Log Tan δ Temperature (ºC) 10 % Styrene 30 % Styrene
-100
-80
-60
-40
-20 20 40 60
Log Tan δ -1 -2 -3
10 % Styrene
30 % Styrene
IBR

20. MVP/PBD (70/30) Log Tan δ Temperature (ºC) IBR 30 % Styrene
-100
-80
-60
-40
-20 20 40 60
Log Tan δ -1 -2 -3
10 % Styrene
30 % Styrene
IBR

21. Acknowledgements
Author would like to thank Goodyear Tire and Rubber Company Management for permission to present this project.
Author would like to thank many His colleagues for their comments and suggestions.