SSBR

New functionalised S-SBRs to meet future tire performance demands
Norbert Steinhauser Alex Lucassen Lanxess Deutschland GmbH

BPRI Conference 2009 Brussels, 25th November
N. Steinhauser \. A. Lucassen 2009-11-25
BPRI Conference 2009
Slide 1
Content
S-SBR: chain-end versus backbone functionalisation
Properties of tyre tread compounds containing backbone functionalised S-SBR lab samples Backbone functionalised high-vinyl S-SBR from production scale: polymer and tyre tread compound properties
Slide 2
Rolling resistance and fuel consumption
Major contributions of energy loss in a passenger car:
Tires rolling resistance: Tyre rubber compounds are viscoelastic They dissipate energy on deformation Contribution to total fuel consumption varies from 15% to 30%
Source: Umweltbundesamt
Slide 3
Slide 4
So NEW European commission directive tire labelling
- Labelling of tyres regarding: Rolling resistance Wet grip Rolling noise - Applies for C1, C2 and C3 tires - Scheduled start: November 2012
Slide 5
Chain-end functionalisation vs. backbone functionalisation
- Li+
polymer chain living chain end
chain-end functionalisation
backbone functionalisation
F F
F F
F: functional group
Slide 6
Chain-end functionalisation vs. backbone functionalisation

site of functionalisation: chain end reduced mobility of chain end improvement of filler dispersion degree of fct. independent of number of chain ends no reduction of degree of fct. with increasing chain length
+: given, resp. advantage
backbone
-: not given, resp. disadvantage
Slide 7
Influence of polymer composition on damping behaviour

State of the art: change of microstructure to improve wet grip leads to deterioriaton in rolling resistance and vice versa
Tan
0,7 0,6 0,5
temperature sweep (vulcanizate) for tyre tread formulation with silica filler
(70 phr S-(S)BR / 30 phr high-cis BR / 90 phr silica)
High-vinyl BR
indicator for:
resp. SBR in formulation: BR

75 0 -37
0,4
tan
wet grip
0,3 0,2 0,1 0,0 -100
rolling resistance
Vinyl [wt.-%] Styrene [wt.-%] Tg [C] Indicator for: Wet grip
SBR
50 24 -15
+ -
-80
-60
-40
-20
20
40
60
80
100
Rolling resist.
temperature [C]
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 8
Influence of chain-end functionalisation on damping behaviour

State of the art: chain-end functionalisation can improve rolling resistance without deteriorating wet grip behaviour
Tan temperature sweep (vulcanizate) for tyre tread formulation with silica filler
(70 phr S-SBR / 30 phr BR / 90 phr silica)
0,7 0,6 0,5 0,4
S-SBR composition: 45 wt.-% vinyl 25 wt.-% styrene without fct. end-group with fct. end-group
tan
indicator for:
0,3
wet grip
0,2 0,1 0,0 -100
rolling resistance
-80
-60
-40
-20
20
40
60
80
100
temperature [C]
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 9
Backbone functionalised S-SBR from Lanxess
Introduction of functional groups of high polarity along the polymer chain
COOH
Method of introduction: radical addition to C-C double bonds in a post-polymerisation reaction
Slide 10
Formulation containing unfunctionalised S-SBR

S-SBR of same microstructure and Tg
Vulcanizate properties of tyre tread formulation with silica filler
0,7 0,6 0,5 0,4
Degree of S-SBR functionalization: no (SBR 1)
indicator for: wet grip rolling resistance
tan
0,3 0,2 0,1 0,0 -120 -100
-80
-60
-40
-20
20
40
60
80
100
temperature [C]
Slide 11
Formulation containing backbone functionalised S-SBR

0,7 0,6 0,5 0,4
Degree of S-SBR functionalization: no (SBR 1) low (SBR 2)
indicator for: wet grip rolling resistance
tan
0,3 0,2 0,1 0,0 -120 -100
-80
-60
-40
-20
20
40
60
80
100
temperature [C]
Slide 12
Formulations containing backbone functionalised S-SBR

0,7 0,6 0,5 0,4
Degree of S-SBR functionalization: no (SBR 1) low (SBR 2) medium (SBR 3) indicator for: wet grip rolling resistance
tan
0,3 0,2 0,1 0,0 -120 -100
-80
-60
-40
-20
20
40
60
80
100
temperature [C]
Slide 13

0,7 0,6 0,5 0,4
Degree of S-SBR functionalization: no (SBR 1) low (SBR 2) medium (SBR 3) high (SBR 4) indicator for: wet grip rolling resistance
tan
simultaneous improvement of indicator for: - wet grip - rolling resist.
0,3 0,2 0,1 0,0 -120 -100
-80
-60
-40
-20
20
40
60
80
100
temperature [C]
Slide 14

Vulcanizate properties of tyre tread formulation (70 phr S-SBR / 30 phr BR / 90 phr silica)
S-SBR No. 1 2 3 4 Degree of funct. no low medium high Tan temp. sweep (1Kmin-1, 10 Hz) tan at 0C 0.232 0.287 0.305 0.436 tan at 60C 0.119 0.112 0.102 0.095
Amplitude sweep: tan max.
Temp. at tan max. [C] -32 -25 -22 -14
Rebound at 60C
[%]
DIN Abrasion
[mm3]
0.211 0.191 0.161 0.145
49.5 54 58.5 59
91 89 81 80
indicator for:
S-SBR 1-4: 40 % vinyl, 24 % styrene Tg (DSC): -33C
wet grip
rolling resistance
abrasion
increasing degree of functionalisation leads to continuous improvement of properties indicative for: - wet grip - rolling resistance - abrasion
Slide 15

tan (0C) 200 190 180 tan (60C) tan max. rebound (60C) DIN abrasion
Relative performance [%]
140 130 120 110 100 90 80
SBR 1
unfct.
SBR 2
low fct.
SBR 3
medium fct.
SBR 4
high fct.
Slide 16
Formulations containing unfunctionalised S-SBR

S-SBR of same Tg and different microstructure
0,7 0,6 0,5 0,4
High-vinyl S-SBR: not fct. (SBR 1) High-styrene S-SBR: not fct. (SBR 5)
unfct. SBR: improvement in - wet grip leads to deterioration in - rolling resistance
tan
indicator for:
0,3 0,2 0,1 0,0 -120 -100
wet grip
rolling resistance
-80
-60
-40
-20
20
40
60
80
100
temperature [C]
Slide 17
Formulation containing backbone functionalised S-SBR

0,7 0,6 0,5 0,4
High-vinyl S-SBR: not fct. (SBR 1) fct. (medium, SBR 3) High-styrene S-SBR: not fct. (SBR 5)
tan
indicator for:
0,3 0,2 0,1 0,0 -120 -100
wet grip
rolling resistance fct. SBR:
simultaneous improvement of - wet grip and

-80 -60 -40 -20 0 20 40 60 80 100
- rolling resistance
temperature [C]
Slide 18

0,7 0,6 0,5 0,4
High-vinyl S-SBR: not fct. (SBR 1) fct. (medium, SBR 3) High-styrene S-SBR: not fct. (SBR 5) fct. (medium, SBR 6)
tan
indicator for:
0,3 0,2 0,1 0,0 -120 -100
wet grip
rolling resistance fct. SBR:
simultaneous improvement of - wet grip and

-80 -60 -40 -20 0 20 40 60 80 100
- rolling resistance
temperature [C]
Slide 19

S-SBR No. Degree of funct. Tan temp. sweep (1Kmin-1, 10 Hz) tan at 0C tan at 60C
Amplitude sweep: tan max.
Temp. at tan max. [C]
Rebound at 60C
[%]
DIN Abrasion
[mm3]
S-SBR in compound: high-vinyl S-SBR (40% vinyl, 24% styrene, Tg: -33C)
1 3
no medium
-32 -22
0.232 0.305
0.119 0.102
0.211 0.161
49.5 58.5
91 81
S-SBR in compound: high-styrene S-SBR (23% vinyl, 38% styrene, Tg: -32C)
5 6
no medium
-21 -11
0.308 0.533
0.128 0.096
0.213 0.155
47 58
101 78
unfct. SBR: change in microstructure (SBR 1
SBR 5) leads to improvement of
indicator for wet grip, but deterioration of indicator for abrasion and rolling resist. fct. SBR: change in microstructure (SBR 3 SBR 6) leads to an overall
improvement of indicators for wet grip, abrasion, and rolling resistance
Slide 20
Backbone functionalised high-vinyl S-SBR from production plant

Polymer properties of S-SBR from production
VSL 5025-2 unfct. Vinyl [wt.-%] Styrene [wt.-%] Tg (DSC) [C] Mooney visc. ML1+4 [MU] MSR [MU/s] Oil content (TDAE) [wt.-%] Mn (GPC) [kg/mol] Mw / Mn COOH functionality [meq./kg] 46 24 -27.5 50 0.482 27.5 373 1.79 PBR 4003 fct. 48 24 -26 53 0.338 28.3 313 2.54 35
Slide 21

Silica compound composition (tyre tread formulation)
unfct. S-SBR (BUNA VSL 5025-2) fct. S-SBR (PBR 4003) High-cis BR (BUNA CB 24) Silica (ULTRASIL 7000 GR) Carbon black (VULCAN J/N 375) TDAE oil (VIVATEC 500) Zinc soap (AKTIPLAST GT) Stearic acid (EDENOR C 18 98-100) Antioxidant (VULKANOX 4020/LG) Antioxidant (VULKANOX HS/LG) Zinc oxide (ZINKWEISS ROTSIEGEL) Wax (ANTILUX 654) Silane (SI 69) Diphenylguanidine (VULKACIT D/C) Benzothiazolesulfenamide (VULKACIT NZ/EGC) Sulphur Sulfonamide (VULKALENT E/C) 96.3 0 30 90 7 10 3.5 1 2 2 2 2 7.2 2.2 1.6 1.6 0.2 0 97 30 90 7 9.3 3.5 1 2 2 2 2 7.2 2.2 1.6 1.6 0.2
Slide 22

Vulcanization behaviour (MDR, 160C)
22 20 18 16 unfct. S-SBR fct. S-SBR
S' [dNm]
14 12 10 8 6 4 2 0 0 200 400 600 800 1000 1200 1400 1600 1800
time [s]
Slide 23

Stress-strain properties (S 2)
22 20 18 16 unfct. S-SBR fct. S-SBR
stress [MPa]
14 12 10 8 6 4 2 0 0 100 200 300 400 500
strain [%]
Slide 24

Tan
0,7 0,6 0,5 0,4
temperature sweep (10 Hz, 1 Kmin-1)

fct. S-SBR
unfct. S-SBR
tan
0,3 0,2 0,1 0,0 -100
-80
-60
-40
-20
20
40
60
80
100
temperature [C]
Slide 25

Tan
0,7
temperature sweep (10 Hz, 1 Kmin-1)

unfct. S-SBR fct. S-SBR 0,14
0,6
0,13
0,12 0,5
tan
0,11 0,4 0,10 0,3
0,09
0,2 -20 -15 -10 -5 0 5 10 15 20 45 50 55 60 65 70 75 80
0,08
temperature [C]
temperature [C]
Slide 26

G and tan amplitude sweep (MTS, 60 C, 1 Hz)
unfct. S-SBR 3,5 fct. S-SBR 0,18
3,0
0,16
2,5
0,14
G' [MPa]
1,5
0,10
1,0
0,08
0,5 0,1 1 10 0,1 1 10
0,06
strain [%]
strain [%]
Slide 27
tan
2,0
0,12

DIN Abrasion 140 tan (0C) tan (60C) tan max. (MTS) Rebound (60C) 140
130
130
Relative Performance [%]
120
120
110
110
100
100
90 unfct. S-SBR fct. S-SBR unfct. S-SBR fct. S-SBR
90
Silica compounds
Carbon black compounds
Slide 28
Backbone functionalised S-SBR
Current state of development

lab studies concerning the influence of microstructure and degree of functionalization completed successful transfer to industrial scale (plant trials)
tyre tests are running for the time being
Slide 29
Summary
Chain-end functionalisation on S-SBR can lead to improvement in rolling resistance without having a major impact on wet grip and abrasion in tire tread formulations Physical lab tests on tire tread formulations with backbone functionalised S-SBR indicate a simultaneous improvement of wet grip and rolling resistance and abrasion First results from tyre tests on backbone functionalised S-SBR confirm the lab test findings
Slide 30
Thank you for your attention!
Slide 31

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New functionalised S-SBRs to meet future tire performance demands

Norbert Steinhauser Alex Lucassen Lanxess Deutschland GmbH

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

S-SBR: chain-end versus backbone functionalisation

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Rolling resistance and fuel consumption

Major contributions of energy loss in a passenger car:

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

So NEW European commission directive tire labelling

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Chain-end functionalisation vs. backbone functionalisation

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Chain-end functionalisation vs. backbone functionalisation

-: not given, resp. disadvantage

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Influence of polymer composition on damping behaviour

resp. SBR in formulation: BR

Influence of chain-end functionalisation on damping behaviour

0,7 0,6 0,5 0,4

Backbone functionalised S-SBR from Lanxess

Introduction of functional groups of high polarity along the polymer chain

Method of introduction: radical addition to C-C double bonds in a post-polymerisation reaction

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Formulation containing unfunctionalised S-SBR

0,7 0,6 0,5 0,4

Degree of S-SBR functionalization: no (SBR 1)

indicator for: wet grip rolling resistance

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Formulation containing backbone functionalised S-SBR

0,7 0,6 0,5 0,4

Degree of S-SBR functionalization: no (SBR 1) low (SBR 2)

indicator for: wet grip rolling resistance

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Formulations containing backbone functionalised S-SBR

0,7 0,6 0,5 0,4

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Formulations containing backbone functionalised S-SBR

0,7 0,6 0,5 0,4

simultaneous improvement of indicator for: - wet grip - rolling resist.

0,3 0,2 0,1 0,0 -120 -100

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Formulations containing backbone functionalised S-SBR

Temp. at tan max. [C] -32 -25 -22 -14

0.211 0.191 0.161 0.145

N. Steinhauser \. A. Lucassen 2009-11-25

BPRI Conference 2009

Formulations containing backbone functionalised S-SBR

Relative performance [%]

140 130 120 110 100 90 80

N. Steinhauser \. A. Lucassen 2009-11-25