ssbr

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


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


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%


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


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


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


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


-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:


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


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


-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:


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


-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


no (SBR 1) low (SBR 2)

tan

temperature [°C]

indicator for:


Formulation containing backbone functionalised S-SBR




-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


no (SBR 1) low (SBR 2) medium (SBR 3)

tan

temperature [°C]

indicator for:


Formulations containing backbone functionalised S-SBR




-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


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.





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




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.





-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:



Formulations containing unfunctionalised S-SBR

unfct. SBR:improvement in- wet grip

leads todeterioration in- rolling resistance

S-SBR of same Tg and different microstructure


-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:



Formulation containing backbone functionalised S-SBR



fct. SBR:simultaneousimprovement of- wet grip

and- rolling resistance



-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:






fct. SBR:simultaneousimprovement of- wet grip

and- rolling resistance



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


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




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


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)



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)



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)



-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)



Tan temperature sweep (10 Hz, 1 K·min-1)


-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


temperature [°C]


G‘ and tan amplitude sweep (MTS, 60 °C, 1 Hz)


0,1 1 100,06

0,08

0,10

0,12

0,14

0,16


tan

strain [%]0,1 1 10

0,5

1,0

1,5

2,0

2,5

3,0

3,5

G'

[MP

a]

strain [%]



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


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


• 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


Thank you for your attention!

ssbr

Documents

tyre tread formulation

wet grip leads

backbone functionalised high

rolling resistance fct

tyre tests

backbone functionalised

rolling resistance

wet grip