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N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 1
New functionalised S-SBRs
to meet future
tire performance demands
Norbert SteinhauserAlex Lucassen
Lanxess Deutschland GmbH
BPRI Conference 2009Brussels, 25th November
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 2
Content
S-SBR:chain-end versus backbone functionalisation
Properties of tyre tread compounds containingbackbone functionalised S-SBR lab samples
Backbone functionalised high-vinyl S-SBR fromproduction scale:polymer and tyre tread compound properties
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 3
Rolling resistance and fuel consumption
Major contributions of energy loss
in a passenger car:
Source: Umweltbundesamt
Tire‘s rolling resistance:
Tyre rubber compounds areviscoelastic
They dissipate energy ondeformation
Contribution to total fuelconsumption varies from15% to 30%
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 4
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 5
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
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 6
Chain-end functionalisation vs. backbone functionalisation
- Li+
polymer chain
backbone functionalisation
F
living chain end
chain-end functionalisation
F
F F
F
F: functional group
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 7
chain end
Chain-end functionalisation vs. backbone functionalisation
backbone
site of functionalisation:
reduced mobilityof chain end
improvement offiller dispersion
degree of fct. independentof number of chain ends
no reduction of degree of fct.with increasing chain length
+
+ +
+
+
-
-
-
+: given, resp. advantage -: not given, resp. disadvantage
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 8
Influence of polymer composition on damping behaviour
-100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
tan
temperature [°C]
indicator for:
wet grip rolling resistance
240Styrene [wt.-%]
-+Rolling resist.
+-Wet grip
Indicator for:
-15-37Tg [°C]
5075Vinyl [wt.-%]
SBRBR
Tan 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 BRresp. SBR in formulation:
State of the art: change of microstructure to improve wet gripleads to deterioriaton in rolling resistance and vice versa
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 9
-100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
tan
temperature [°C]
S-SBR composition:45 wt.-% vinyl25 wt.-% styrene
without fct. end-group with fct. end-group
indicator for:
wet grip rolling resistance
Influence of chain-end functionalisation on damping behaviour
Tan temperature sweep (vulcanizate) for tyre tread formulation with silica filler(70 phr S-SBR / 30 phr BR / 90 phr silica)
State of the art: chain-end functionalisation can improverolling resistance without deteriorating wet grip behaviour
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 10
Backbone functionalised S-SBR from Lanxess
S
COOH
Introduction of functional groups of high polarity along the polymer chain
Method of introduction: radical addition to C-C double bondsin a post-polymerisation reaction
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 11
-120 -100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7Degree of S-SBRfunctionalization:
no (SBR 1)
tan
temperature [°C]
indicator for:
wet grip rolling resistance
Vulcanizate properties of tyre tread formulation with silica filler(70 phr S-SBR / 30 phr BR / 90 phr silica)
Formulation containing unfunctionalised S-SBR
S-SBR of same microstructure and Tg
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 12
-120 -100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7Degree of S-SBRfunctionalization:
no (SBR 1) low (SBR 2)
tan
temperature [°C]
indicator for:
wet grip rolling resistance
Formulation containing backbone functionalised S-SBR
S-SBR of same microstructure and Tg
Vulcanizate properties of tyre tread formulation with silica filler(70 phr S-SBR / 30 phr BR / 90 phr silica)
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 13
-120 -100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7Degree of S-SBRfunctionalization:
no (SBR 1) low (SBR 2) medium (SBR 3)
tan
temperature [°C]
indicator for:
wet grip rolling resistance
Formulations containing backbone functionalised S-SBR
S-SBR of same microstructure and Tg
Vulcanizate properties of tyre tread formulation with silica filler(70 phr S-SBR / 30 phr BR / 90 phr silica)
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 14
-120 -100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7Degree of S-SBRfunctionalization:
no (SBR 1) low (SBR 2) medium (SBR 3) high (SBR 4)
tan
temperature [°C]
indicator for:
wet grip rolling resistance simultaneousimprovementof indicator for:- wet grip- rolling resist.
Formulations containing backbone functionalised S-SBR
S-SBR of same microstructure and Tg
Vulcanizate properties of tyre tread formulation with silica filler(70 phr S-SBR / 30 phr BR / 90 phr silica)
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 15
S-SBR 1-4:40 % vinyl,24 % styreneTg (DSC): -33°C
Vulcanizate properties of tyre tread formulation (70 phr S-SBR / 30 phr BR / 90 phr silica)
0.145
0.161
0.191
0.211
Amplitudesweep:
tan max.
80590.0950.436-14high4
8158.50.1020.305-22medium3
89540.1120.287-25low2
9149.50.1190.232-32no1
DINAbrasion
[mm3]
Reboundat 60°C
[%]tan
at 60°Ctan
at 0°C
Temp. attan
max. [°C]
Degreeof
funct.No.
Tan temp. sweep (1K·min-1, 10 Hz)S-SBR
increasing degree of functionalisation leads tocontinuous improvement of properties indicative for:
- wet grip - rolling resistance - abrasion
indicator for: wet grip rolling resistance abrasion
Formulations containing backbone functionalised S-SBR
S-SBR of same microstructure and Tg
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 16
80
90
100
110
120
130
140
180
190
200
high fct.medium fct.unfct.SBR 4SBR 3SBR 2
Rel
ativ
e pe
rform
ance
[%
] tan (0°C) tan (60°C) tan max. rebound (60°C) DIN abrasion
SBR 1low fct.
Formulations containing backbone functionalised S-SBR
Vulcanizate properties of tyre tread formulation (70 phr S-SBR / 30 phr BR / 90 phr silica)
S-SBR of same microstructure and Tg
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 17
-120 -100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
tan
temperature [°C]
High-vinyl S-SBR:not fct. (SBR 1)
High-styrene S-SBR: not fct. (SBR 5)
indicator for:
wet grip rolling resistance
Vulcanizate properties of tyre tread formulation with silica filler(70 phr S-SBR / 30 phr BR / 90 phr silica)
Formulations containing unfunctionalised S-SBR
unfct. SBR:improvement in- wet grip
leads todeterioration in- rolling resistance
S-SBR of same Tg and different microstructure
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 18
-120 -100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
tan
temperature [°C]
High-vinyl S-SBR: not fct. (SBR 1) fct. (medium, SBR 3)
High-styrene S-SBR: not fct. (SBR 5)
indicator for:
wet grip rolling resistance
Vulcanizate properties of tyre tread formulation with silica filler(70 phr S-SBR / 30 phr BR / 90 phr silica)
Formulation containing backbone functionalised S-SBR
unfct. SBR:improvement in- wet grip
leads todeterioration in- rolling resistance
fct. SBR:simultaneousimprovement of- wet grip
and- rolling resistance
S-SBR of same Tg and different microstructure
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 19
-120 -100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
tan
temperature [°C]
High-vinyl S-SBR: not fct. (SBR 1) fct. (medium, SBR 3)
High-styrene S-SBR: not fct. (SBR 5) fct. (medium, SBR 6)
indicator for:
wet grip rolling resistance
Vulcanizate properties of tyre tread formulation with silica filler(70 phr S-SBR / 30 phr BR / 90 phr silica)
Formulations containing backbone functionalised S-SBR
unfct. SBR:improvement in- wet grip
leads todeterioration in- rolling resistance
fct. SBR:simultaneousimprovement of- wet grip
and- rolling resistance
S-SBR of same Tg and different microstructure
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 20
S-SBR in compound: high-vinyl S-SBR (40% vinyl, 24% styrene, Tg: -33°C)
S-SBR in compound: high-styrene S-SBR (23% vinyl, 38% styrene, Tg: -32°C)
0.155
0.213
0.161
0.211
Amplitudesweep:
tan max.
78580.0960.533-11medium6
101470.1280.308-21no5
8158.50.1020.305-22medium3
9149.50.1190.232-32no1
DINAbrasion
[mm3]
Reboundat 60°C
[%]tan
at 60°Ctan
at 0°C
Temp. attan
max. [°C]
Degreeof
funct.No.
Tan temp. sweep (1K·min-1, 10 Hz)S-SBR
Formulations containing backbone functionalised S-SBR
unfct. SBR: change in microstructure (SBR 1 SBR 5) leads to improvement ofindicator for wet grip, but deterioration of indicator for abrasion and rolling resist.
fct. SBR: change in microstructure (SBR 3 SBR 6) leads to an overallimprovement of indicators for wet grip, abrasion, and rolling resistance
Vulcanizate properties of tyre tread formulation (70 phr S-SBR / 30 phr BR / 90 phr silica)
S-SBR of same Tg and different microstructure
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 21
Polymer properties of S-SBR from production
0.3380.482MSR [MU/s]
35-COOH functionality [meq./kg]
2.541.79Mw / Mn
313373Mn (GPC) [kg/mol]
28.327.5Oil content (TDAE) [wt.-%]
5350Mooney visc. ML1+4 [MU]
-26-27.5Tg (DSC) [°C]
2424Styrene [wt.-%]
4846Vinyl [wt.-%]
PBR 4003fct.
VSL 5025-2unfct.
Backbone functionalised high-vinyl S-SBR from production plant
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 22
9090Silica (ULTRASIL 7000 GR)
970fct. S-SBR (PBR 4003)
096.3unfct. S-SBR (BUNA VSL 5025-2)
0.20.2Sulfonamide (VULKALENT E/C)
1.61.6Sulphur
1.61.6Benzothiazolesulfenamide (VULKACIT NZ/EGC)
2.22.2Diphenylguanidine (VULKACIT D/C)
7.27.2Silane (SI 69)
22Wax (ANTILUX 654)
22Zinc oxide (ZINKWEISS ROTSIEGEL)
22Antioxidant (VULKANOX HS/LG)
22Antioxidant (VULKANOX 4020/LG)
11Stearic acid (EDENOR C 18 98-100)
3.53.5Zinc soap (AKTIPLAST GT)
9.310TDAE oil (VIVATEC 500)
77Carbon black (VULCAN J/N 375)
3030High-cis BR (BUNA CB 24)
Silica compound composition (tyre tread formulation)
Backbone functionalised high-vinyl S-SBR from production plant
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 23
0 200 400 600 800 1000 1200 1400 1600 18000
2
4
6
8
10
12
14
16
18
20
22 unfct. S-SBR fct. S-SBR
S'
[dN
m]
time [s]
Vulcanization behaviour (MDR, 160°C)
Backbone functionalised high-vinyl S-SBR from production plant
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 24
0 100 200 300 400 5000
2
4
6
8
10
12
14
16
18
20
22 unfct. S-SBR fct. S-SBR
stre
ss
[MPa
]
strain [%]
Stress-strain properties (S 2)
Backbone functionalised high-vinyl S-SBR from production plant
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 25
-100 -80 -60 -40 -20 0 20 40 60 80 1000,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7 unfct. S-SBR fct. S-SBR
tan
temperature [°C]
Tan temperature sweep (10 Hz, 1 K·min-1)
Backbone functionalised high-vinyl S-SBR from production plant
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 26
Tan temperature sweep (10 Hz, 1 K·min-1)
Backbone functionalised high-vinyl S-SBR from production plant
-20 -15 -10 -5 0 5 10 15 200,2
0,3
0,4
0,5
0,6
0,7
tan
temperature [°C]45 50 55 60 65 70 75 80
0,08
0,09
0,10
0,11
0,12
0,13
0,14 unfct. S-SBR fct. S-SBR
temperature [°C]
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 27
G‘ and tan amplitude sweep (MTS, 60 °C, 1 Hz)
Backbone functionalised high-vinyl S-SBR from production plant
0,1 1 100,06
0,08
0,10
0,12
0,14
0,16
0,18 unfct. S-SBR fct. S-SBR
tan
strain [%]0,1 1 10
0,5
1,0
1,5
2,0
2,5
3,0
3,5
G'
[MP
a]
strain [%]
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 28
Backbone functionalised high-vinyl S-SBR from production plant
90
100
110
120
130
140
Rel
ativ
e P
erfo
rman
ce
[%]
Silica compounds
DIN Abrasion tan (0°C) tan (60°C) tan max. (MTS) Rebound (60°C)
90
100
110
120
130
140
fct. S-SBRfct. S-SBR unfct. S-SBRCarbon black compounds
unfct. S-SBR
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 29
Backbone functionalised S-SBR
Current state of development
• lab studies concerning the influence of microstructureand degree of functionalization completed
• successful transfer to industrial scale (plant trials)
• tyre tests are running for the time being
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 30
• Chain-end functionalisation on S-SBR can lead toimprovement in rolling resistance without having a majorimpact on wet grip and abrasion in tire tread formulations
Summary
• Physical lab tests on tire tread formulations withbackbone functionalised S-SBR indicate a simultaneousimprovement of wet grip and rolling resistance and abrasion
• First results from tyre tests on backbone functionalised S-SBRconfirm the lab test findings
N. Steinhauser \. A. Lucassen 2009-11-25 BPRI Conference 2009 Slide 31
Thank you for your attention!