1. The Title is Trans-SBR a Crystallizable Elastomer
Rubber Division Presentation
Akron Ohio, April 27, 2010
This a presentation was given at the Rubber Division Spring meeting 2010
The Title is Trans-SBR a Crystallizable Elastomer
Adel F Halasa
The Goodyear Tire & Rubber co.

2. Agenda Objectives. Catalyst System. Catalyst Preparation
Polymerization
Batch
Continuos
Polymer Characterization
Polymer Properties

3. Objectives
The Objectives of this research is to prepare new polymers with crystalline unites & control Microstructures& sequence distributions that open the door to a new viscoelastic behavior
Improve traction
Improve wear
reduced rolling resistance

4. Objectives Continued Better adhesion
Reduced Chipping and chunking in RMT
Improved tear strength
Building tack
Improved dimensional stability
Improved durability

5. Conjugated Diene Microstructures
Butadiene 1,4-Trans 1,4-Cis 1,2/V
Wear
Traction RR
Isoprene
Wear
Traction RR

6. Strain crystallizes Polymers
Reduces chipping/chunking damage in RMT, farm application,stump penetration OTR
Low hysteresis
Lower running Temperature
Sufficient green strength
good tire building properties
less shrinkage
dimensional stability

7. Barium Catalyst System Comparison
Microstructure Tg
(oC) Tm
Copolymerize Styrene
trans-1,4
cis-1,4
1,2
Ziegler-Natta 80 4 16
-75 40 NO
Alfin 77 23
-67
YES
Ba/Mg/Al
70-90
27-7 3
-90

8. Background Of Trans Polymers
Alfin catalyst
Ally Sodium/Sodium Chloride/Sodium Isoproxide ( 1/1/1)
Extremely high molecular weight difficult to process
Co-polymerize styrene and butadiene
Styrene incorporation is 10% Max.
Co-polymer has 30 to35% Vinyl
difficult to oil extend due to the extreme molecular weight

9. Background continued Potassium system
Potassium tert-Amyloxide (KOAM)/ R2Mg
KOAm/R3MgK
KOAM/TMEDA/R3MgK (3/1/1)
PBD 98% Trans structures
resin form-need a hot house to process
Do not co-polymerize styrene to form trans structures but form 1,2 co-polymer

10. Background Continued Transition Metals catalyst
Cobalt Octoate/TIBAL/Nonylphenolate( 1/10/10)
Does not form copolymers of styrene or Isoprene
Tg of PBD -75ºC
Highly crystalline structure need hot housing
Tm +40ºC

11. Barium System
Barium alkoxide in combination with dialkymagnesium or Aluminum alkyls have been used to co-polymerize styrene and butadiene with trans structures
J.G. Hargis, et al., Acs Symp ser 1982, 193 ( Elastomers and rubber Elasticity),
Barium alkoxide usually are made from Barium metal in liquid ammonia and the corresponding alcohol

13. Barium System Our discovery:
Cheaper method of making Barium compounds from Barium hydroxide
The use of Organo-lithium in conjunction with Aluminum alkyls
The use of polar modifiers to increase the Trans-contents and at faster reaction rates at higher temperatures

14. Barium System continued.
Our Procedure
Barium metal = $ 110/lb.
Ba(OH)2 + DEGEE =
Ba(OH)2 + THFA= Ba(OR)2 + H2O
Ba(OH)2 + Thymol=
Barium Hydroxide monohydrate =($0.30)
DEGEE ( Di (ethylene glycol) Alkyl ethers

15. Barium System Catalyst Components: Optimal ratios 1/4/3 Ba(OR)2
Barium Alkoxires
Trioctyl aluminum(TOA)
n-butyllithium( BuLi)
Optimal ratios 1/4/3 Ba(OR)2

31. NMR Analysis
Solution 400 MHz C-13 and H-1 NMR were used to determine the SBR composition, Bd microstructure, and styrene sequencing.

33. Continuos polymerization

34. TRANS_POLYMER

44. Tm verses Trans-Content(PBD)

45. Trans-PBD Morphoploy

46. Tm Verses Trans-Contents

50. Trans-SBR

51. TRANS_SBR