Influence of functionalized S-SBR on silica-filled rubber ... · Influence of functionalized S-SBR...
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Influence of functionalized S-SBR on silica-filled rubber compound properties C. Yamada 1,2 , A.Yasumoto 2 , J.W.M. Noordermeer 1 , W.K. Dierkes 1 , A. Blume 1 1 University of Twente, Dept. of Elastomer Technology and Engineering (the Netherlands) 2 Asahi Kasei Corp. (Japan) 1 2 Tire market performance requirements EU Japan US (planned) Korea High Fuel (ႈFLHQF\ (RR) Better Wet Grip Wear Resistance Tire labeling CO2 emission legislation (OE) eco tire share in Japan 2010 45% ĺ 2013 70% Strong demand for improving overall performance This document is only for the exclusive use by attendees of the DKT 2018 scientific conference. Passing on to third parties or publishing the contents or parts of the contents requires the express consent of the author(s).
Transcript of Influence of functionalized S-SBR on silica-filled rubber ... · Influence of functionalized S-SBR...
Influence of functionalized S-SBR on silica-filled rubber compound properties
C. Yamada1,2, A.Yasumoto2, J.W.M. Noordermeer1, W.K. Dierkes1, A. Blume1
1 University of Twente, Dept. of Elastomer Technology and Engineering (the Netherlands)2 Asahi Kasei Corp. (Japan)
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2
Tire market performance requirements
EU Japan
US (planned)Korea
High Fuel(RR)
BetterWet Grip
WearResistance
Tire labeling CO2 emissionlegislation (OE)
eco tire share in Japan2010 45% 2013 70%
Strong demand for improving overall performance
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KT 2018 scientific conference. Passing on to third parties or publishing the contents or parts of the contents requires the express consent of the author(s).
3
Rubber for Tread of Tire
Tread
Tread
Performance Material
Low-RRGripWear resistance
SBRNRBRFiller (Silica)Oil
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E-SBR and S-SBR
S-SBR (Solution SBR) Solution-polymerized Styrene Butadiene RubberE-SBR (Emulsion SBR) Emulsion-polymerized Styrene Butadiene Rubber
E-SBR S-SBR
Process Emulsion Solution
Polymerization Radical Anionic
Styrene (%) 0 – 50 % Controllable (0 90 %)
Styrene Chain Random Controllable(Random Block)
Vinyl in Butadiene 15 – 18% Controllable (0 80%)
Functionalization Introduce 3rd monomer Chain end
Branching Multi branched Controllable(linear multi branched)
MW distribution Wide Controllable(Wide narrow)
Saito, A.: Nippon Gomu Kyokaishi, 71, 41(1998)
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How to improve S-SBR?
Advantages Bad point
Macro structure High molecular weight (less free chain ends) Lower tan Lower
Processability
Narrow molecular distribution (less free chain ends) Lower tan Lower
Processability
Less branch or graft structure(less free chain ends) Lower tan Lower
Processability
Microstructure Low vinyl content(lower Tg) Lower tan Lower grip
Low styrene content(lower Tg) Lower tan Lower grip and
processability
Functionalization Less free chain ends Lower tan(Good filler dispersion)
Lowerprocessability
Saito, A.: Nippon Gomu Kyokaishi, 71, 41(1998)
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How to introduce functional group in S-SBR?
1. Functionalization of the chain end
2. Functionalization of initiator
3. Functionalization of main chain with functionalized monomer
4. Functionalization of side chain
SBR Functional Group
+
-Li+
Initiator
+ Styrene + Butadiene
Polymerization
Functionalized monomer
Polymerization
C-Li+
Styrene + Butadiene +
SBR
+
Functional Group
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The aim of this study
Alkoxy amine groupAmine group
Effect Method
1 Silica micro dispersion TEM, USAX
2 Flocculation of filler RPA2000
3 Filler-polymer interaction Bound rubber, Payne effect
Mw (kg/mol) 240-280
ML (100C) 42-47
Styrene (wt%) 27
Vinyl (wt%) 42-43
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Formulation, mixing procedure and cure condition
Formulation (phr)
SBR 80
BR (UBEPOL BR150) 20
Silica (ULTRASIL 7000GR) 75
TESPT 5.6
TDAE oil (total) 33
Zinc Oxide 2.5
Stearic Acid 2.0
Antioxidant (6PPD) 2.0
Sulfur 2.2
CBS 1.7
DPG 2.0
Master batch (MB1) BrabenderTime0:00 Add Polymers0:20 Mix1:20 1/2 Silica, 1/2 TESPT, Oil1:50 Mix2:50 1/2 Silica, 1/2 TESPT, Stearic Acid, Zinc Oxide3:10 Mix (Control rpm. up to target temp.)4:10 Ram sweep6:40 Discharge (145-150 Co)
Master batch (MB2) Brabender0:00 Add MB14:00 Discharge (145-150 Co)
Final Mix (Productive) Roll (50°C)MB2 + Sulfur and Accelerators
Cure conditionTemp 160 Co
Time t90
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Payne effect of uncured compounds
0
50
100
150
200
250
300
350
400
450
500
0,1 1 10 100 1000
G' [
kPa]
Strain [%]
Alkoxy group
Amine group
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USAX measurement
])}6/({)}()({/3})3(exp{-[)( )6()6(32
22
2 DsDssilicasilicand
Dmnd qqrerfBqMIqIqrqAnqI
fractal structure at small angle
Secondary agglomeration
fractal structure at large angle
A,B constantn Number density of secondary aggregatesM number of primary particles in the secondary aggregater2nd, rsilica secondary aggregate, average primary radius of silica primary particleDm, Ds fractal dimension at small and wide angleI2nd(q) Scattering equation of the same structure with uniform internal size and secondary aggregates
Electron density difference [v* silica+(1-v)* polymer)] – polymer
v silica volume fraction in the secondary aggregateIsilica(q) When the structure in the secondary aggregate is infinitely spread
Inte
nsity
q (nm-1)
Solid line measured lineDotted line fitted line
compound
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USAX result and TEM images
<
••
Average silica size from USAX profile (nm)
500nm500nm500nm
Alkoxy group
Amine group
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Payne effect of uncured compounds
0
50
100
150
200
250
300
350
400
450
500
0,1 1 10 100 1000
G' [
kPa]
Strain [%]
Alkoxy group
Amine group
0
0
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13
Comparison the result of payne effect and USAX
Polymer-networkContributionHydrodynamic effect
Strain
|G*|
Polymer-networkContributionHydrodynamic effect
Strain
|G*|
Non-functionalized SBRFunctionalized SBR
Filler-fillerinteraction
Filler-polymerinteraction
Filler-fillerinteraction
Filler-polymerinteraction
Normal one
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Measurement bound rubber
Bound rubber1. Occluded rubber2. Gel3. Rubber connecting via
hydrogen bonding4. Rubber connecting via
covalent bonding
Chemical bound rubber1. Gel2. Rubber connected with
silica via covalent bonding
Physical bound rubber1. Occluded rubber2. Rubber connected with
silica via hydrogen bonding
Phy BR Rubber weekly connected to silicaChem BR Rubber strongly connected to silica
connected with silica via hydrogen bonding connected with silica via covalent bonding
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Bound Rubber of uncured compound
Alkoxy group
Amine group
0
10
20
30
40
50
60
Bou
nd ru
bber
[wt%
]
Phy BRChem BR
0
50
100
150
200
250
300
350
400
450
500
0,1 1 10 100 1000
G' [
kPa]
Strain [%]
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Payne Effect After Cure
0
1000
2000
3000
4000
5000
0,1 1 10 100 1000
G' (
100
Co )
[kP
a]
Strain [%]
Alkoxy group
Amine group
00
000Cured Uncured
0
0
0
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Flocculation
Alkoxy group
Amine group
0
200
400
600
800
1000
1200
0 2 4 6 8 10 12
G' /
kPa
time / min
Temp 100CStrain 0.5%
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Payne Effect After Cure
0
50
100
150
200
250
300
350
400
450
500
0,1 1 10 100 1000
G' [
kPa]
Strain [%]
0
1000
2000
3000
4000
5000
0,1 1 10 100 1000
G' (
100
Co )
[kP
a]
Strain [%]
Alkoxy group
Amine group
00
000Cured Uncured
0
0
0
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KT 2018 scientific conference. Passing on to third parties or publishing the contents or parts of the contents requires the express consent of the author(s).
0,00
0,02
0,04
0,06
0,08
0,10
tan
(60
o C)
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tan
0
0,5
1
-80 -60 -40 -20 0 20 40 60 80 100
tan
Temperature [oC]
Alkoxy group
Amine group
30/6/18 20
Why tan peak is higher in functionalized SBR compound?
Worse dispersionMore occluded rubber
Better dispersionless occluded rubber
Silica particle can move with rubber under the deformation
Only rubber can move under the deformation
No or week interaction with silica Strong interaction with silica
Alkoxy group
Amine group
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21
The Summery
Effect How to analyze Amine group Alkoxy group
Silica dispersion TEM, USAX + +++
Flocculation of filler RPA2000 + +++
Filler-polymerinteraction
Bound rubberPayne effect + +++
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KT 2018 scientific conference. Passing on to third parties or publishing the contents or parts of the contents requires the express consent of the author(s).
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