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Solution Solution SBRs SBRs for Silica tirefor Silica tireAsahi Kasei Corporation Asahi Kasei Corporation
Synthetic Rubber DivisionSynthetic Rubber Division
August, 15, 2001
2 page
Rubber business of AsahiRubber business of Asahi•• Kawasaki Plant Kawasaki Plant
(Asahi Chemical)• Capa:150Kton/Y• Tech:Firestone(1964)• Process: Continuous
&Batch• Product:
Low cis BR(PS&Rubber)Sol-SBR (Rubber)
SB-TPE Hydrogenated TPE Transparent Resin
•• Oita PlantOita Plant(Japan Elastomer)
• Capa:60Kton/Y• Tech:Phillips(1968)• Process: Bach
• Product: Low cis BR (PS)
Sol-SBR((PS&Rubber)
SB-TPE Hydrogenated TPE Transparent Resin
August. 2001
OE-SBR(TufdeneTM) for tire
Grade St/Vi ML Oil(phr) Characteristics
1534 18/13 45 37.5 Abrasion resistance 2530 25/13 40 37.5 Good Processability 3330 31/30 65 37.5 RR/Wet grip balance 3335 36/33 55 37.5 High Grip 4350 39/38 42 50 High grip
Green : Conventional type Red : Performance type(Medium Vinyl)
August. 2001 3 page
4 pageGrip
LRR
good ↑
→ good
HP Tire(2nd)
~1980
LRR Tire(2nd)
LRR Tire
(3rd)
HP Tire(3nd)
HP Tire
(1st)
LRR Tire(1st)
~2000
~1995
2000
Market trend of PC-Tire
MarketDemand
ConventionalRadial Tire
Silica
CB Age
Silica Age
Demands for LRR/Grip balance are increasing year by year and will continue forever.
Drastic change after "Green Tire " with Silica. (in EU and Japan after)
Uninterrupted Improvement of Materails is requireing from Market
August. 2001
5 page
Material Improvement for PC/Tire tread
C/B Age Silica Age1975 1985 1995 2000
DryS-SBR
OES-SBR
Em-SBR
Sn-Coupled HiVinyl SBR(Ba.) Sn +N-mod.HiVinyl SBR(Ba.)
E-10(Ba.)[Modified-SBRAsahi]
T-3330,3335,4350(cont.)[Asahi- MV-SBR]
VSL5025,5525(cont.)[Bayer-HV-SBR]
Goodyear SIBR
E-50&60(Cont.)[Modified-SBR,Asahi]
Hi-Styrene Em-SBRNote: (Ba.)= Batch Polymzn.process (Cont.)=Continous 〃
August. 2001
August 2001. By Asahi-KASEI
Table A. Asahi's Solution SBR Line-up for Silica Tire Compound
2nd stage 3rd stageConventionalGrade
Now Developing Characteristics
Type (Application)Smallmodification
Supermodification
Dry LRR (low filer & low oil) -25 to -35°C - E-10 Super Wet-RRbalance
( 39 / 31 ) High strength
OEWinterHi-performance Tire
-35 to -45°C Tufdene 3330
( 31 / 30 ) E-50 Good Wet-RR-
SummerHi-performance Tire
-25 to -35°C Tufdene 3335 ( 35.5 / 33 ) winter balance
( 35.5 / 33 )
E-60UltraHi-performance Tire
-15 to -25°C Tufdene 4350 ( 33/ 53 )Super Dry and Wet grip
( 39 / 38 )
( styrene / vinyl )
6 pageAugust. 2001
Tg vs RR of Asahi's OE-SSBR Line-up in Silica tire conpound
0.10
0.15
0.20
0.25-60 -50 -40 -30 -20 -10
[Good ← Low temp. Prop] Tg of SBR(℃, DSC mid) [Grip → Good]
Tan
δ@
50℃
, S
ilic
a O
E c
om
po
un
d R
R →
Go
od
E-50Asahi Super modifid SBR
Good
T4350
T3335
T3330
Asahi MV-SBR (Conventional for silica)
EmulsionS B R
CommercalHV-SBR
E-60
CompoundSBR/ A-oil/ VN-3/N339=100/ 37.5/ 63 / 7
August. 2001 7 page
Characteristics of E-50 & E-60
A. Characteristics of Polymer structure
1.Specified Chemical modifications on Solution SBR for silica compound to improve silica/ rubber interaction
2. High Tg SBR by well balanced Random Styrene and Vinyl content
3. High molecular weight with medium Mw/Mn
B. Characteristics in silica compounds
1. Good hysteresis loss properties, a. lower Tanδ in high temperature, higher Tanδ in low temperature. → Good RR-Grip balance, good Low temp. prop(Softness)-Grip balance. b. Payne effects(strain dependence of G' and Tanδ) reduced → Good dispersion of fillers or good interaction of silica/rubber.
Asahi thinks improvement of above hysteresis loss properties are caused by increase of silica / rubber interaction and increase of bound rubber content.
3. Possibilities to reduce of Silane coupling agent(Si69 ) content.
8 pageAugust. 2001
August 2001Asahi-Kasei Corporation
Table . List of SSBR grade of Asahi for Silica compound
Gra d eAroma.oil ( ph r )
ML1+4,100℃,(Dry)
ML1+4,100℃,(OE)
Styrene(wt%)
Vinyl (%in BD)
Tg (℃,mid point,byDSC)
Mw/ Mn(typica l )
Modifica t ion Remark
OE E-50 37.5 - 72 35.5 33 -30 2.3 Super
E-60 37.5 - 70 33 52 -19 2.3 Super
Tuf de n e3330 37.5 - 65 31 30 -40 2.4 Small
OE Tuf de n e 3335 37.5 - 55 35.5 33 -30 2.4 Small Many
custome r s
Tuf de n e4350 50 - 42 39 38 -22 2.4 Small
in J apa n , EU & Asia
Dry E-10 0 72 - 39 31 -28 1.4 Super New p r o du c t
( All data are typical value and not the specification)
9 page
New product
August. 2001
Fig. Grade Map of S-SBR Line-up of Asahi (styrene and vinyl)
0
5
10
15
20
25
30
35
40
45
50
0 10 20 30 40 50 60 70 80 90
Vinyl (% in BD) (not % in total polymer)
Sty
ren
e (w
t%)
Asahi/ LV-SBR
Asahi/MV-SBR
TufdeneE (modified)
AsapreneE (modified)
Commercial
Commercial
Commercial
E-SBR
E-50
T3330
T4350
E-60
T2530
T3335
T1534
A531
Tg value : Mid point of DSC
Tg=-7 C00000000000000 0 Tg=-5 C00000000000000 0Tg=-3 C00000000000000 0 Tg=-1 C00000000000000 0
A1204
E-10
August. 200110 page
Model scheme of Modification and Coupling reaction by Mulifunctional regent
BuLi+Butadiene+Styrene → (Polymerization)
Asahi's n(SBR-Li) + X(-R-C-C)4 → X-(R-C-C-SBR)4 (+SBR-Li)Case ∨ |
O O-Li (impurity part)Couplend/Modified part
Case 1. Referenece (SnCl4 or Si Cl4 coupl in g )
4(SBR-Li) + SnCl4 → Sn-SBR4 +LiCl4 + SBR-Li
Sn-Couplend /Sn-Modified (impurity part)
Case 2. Referenece (SnCl4 coupling + mono-functional reagent)
4(SBR-Li) + SnCl4 + Z(-R'=Y) → Sn-SBR4 +LiCl4 + SBR-R'-YlLi +SBR-Li Z (impurity part)
Sn-Couplend /Sn-Modified
Function-Modified
11 pageAugust. 2001
Advatages of Asahi's modification
50
100
150
200Com
p M
L(10
0℃)
Bou
nd R
ubbe
r
M30
0% Tb Eb
Reb
@70
℃
G' 0
℃,0
.1%
Tan
δ0℃
,0.1
%
Tan
δ0℃
,3%
Tan
δ50
℃,3
%
Inde
x(La
rge
valu
e is
pre
fera
ble)
Asahi- typeSiCl4
Compound recipe:SBR/ A-oil/ Silica/ N339/ Si69/ S=100/ 37.5/ 63/ 7/ 6.3/ 1.1
Effect of Asahi's Modification
1) Increse of bound rubber. → Improvement of filler dispersion
2) Improvement of hysterisis loss → Better LRR/Grip balance
12 page
August. 2001
Fig Change of Payne effect by Asahi's Functional Group
Comparison of Modification-Silica compound / Tanδ @50℃ strain dependence
VN3/N339=63/7)(
0.05
0.10
0.15
0.20
0.25
0.1 1.0 10.0
Strain (%)
@50
℃-t
anδ
Asahi-Type
SiCl4
Comparison of Modification-Silica compound / G' @50℃ strain dependenced /
VN3/N339=63/7 )(
1.0
10.0
0.10 1.00 10.00
Strain(%)
50℃
-G'
(MPa) Asahi-Type
SiCl4
Comparison of Modification-Silica compound /Tanδ @0℃ strain dependence
VN3/N339=63/7)(
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
0.1 1.0 10.0
strain(%)
0℃-t
anδ
Asahi-Type
SiCl4
Comparison of Modification-Silica compound / G' @0℃ strain dependence /
VN3/N339=63/7 )(
1.0
10.0
100.0
0.10 1.00 10.00
strain(%)
0℃-G
' (M
Pa)
Asahi-TypeSiCl4
August. 2001
Page 13
At 50 C゚
Δ G' SiCl4 cup. > Asahi Coup
Δ Tanδ SiCl4 cup. > Asahi coup.
→ Asahi' type coupling makes better filer dispersiom and lower RR.
At 0 C゚
ΔG' SiCl4 cup. < Asahi Coup
ΔTanδ SiCl4 cup.<< Asahi coup. Same Tg range but Tanδ are grate differenec. asahi coupling makes better
wet grip and loe temperature
hardness.
0
0. 2
0. 4
0. 6
13 15 17 19 21 23 25 27 29Ti me (mi n)
T3330
E-50
E-60
SBR1712
GPC-Curve of Asahi's S-SBR
August. 2001
Page 14
Asahi modified SBR vs. Commercial HV-SBR
50
100
150
200B
ou
nd
Ru
bb
er
Co
mp
d.
M.
Vis
.
M3
00
%
M3
00
/M1
00
Te
ns
ile
str
en
gth
Elo
ng
ati
on
(%
)
Re
b.
@5
0°C
G'@
0°C
0.1
%
Ta
nδ
@0
°C
0.1
%
Ta
nδ
@0
°C,
3%
Ta
nδ
@5
0°C
, 3
%
ΔG
' @5
0°C
Ind
ex
(L
arg
e i
s p
refe
rab
le)
T-3330E-50E-60HV-SBR
August. 2001
Index= 287
Index= 256
Index= 200
Advantages of Asahi Modified SBR
1) Increased bound rubber and good silica dispersion
2) Good mechanical properties
3) Low hysteresis loss at higher temperature
4) Good LRR/Grip balance
5) Soft around C00000000000000 0
Page 15
Tanδ @ 0°C 0.1% strain vs Tanδ @ 50°C 3% strain
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Tanδ @ 0°C 0.1% strain Grip → Good
Tan
δ
@ 5
0°C
3%
str
ain
LR
R →
Go
od
August 2001
E50
E60
HV-SBR/Ger
T3330
T3335
Compd recipeSBR=100 A-oil=37.5
Silica-VN3=63 N339=7Si69=6.3
Good
Note:
LRR/ Wet grip balance・ (= Tanδ 5 C/ Tanδ C)0 0000000000000000000000000000 0
E-50 & E-60 > T-3330 & T-3335 >=HV-SBR/Ger
LRR properties of E-50 is very attractive
Page 16
Tanδ @ 0°C 0.1% strain vs G'@ 0°C 0.1% strain
10
15
20
25
30
35
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Tanδ @ 0°C 0.1% strain
G'
@ 0
°C
0.1%
str
ain
(P
a)
August 2001
E50
E60
HV-SBR/Ger
T3330
T3335
Good
Compd recipeSBR=100 A-oil=37.5
Silica-VN3=63 N339=7Si69=6.3
Note:
Low temp hardness/・ Wet grip balance (= G' at C/ Tanδ C)0 0000000000000000000000000000 0
E-50 & E-60 > T-3330 & T-3335 > HV-SBR/Ger
G' at low temperaure of・ Asahi SSBR are lower than commecial HV-SBR because of good filler disper si o n
Page 17
Visco-Elasitic cure of E-50, E60,T3335,T3330 & HV-SBR
0.0
0.2
0.4
0.6
0.8
1.0
1.2
-50 -40 -30 -20 -10 0 10 20 30 40 50 60 70Temp(℃)
tanδ
,(-)
[Measured by reometrix Ares,10Hz,strain=1.0%]
HV-SBR
T3335
E-60
T-3330
E-50
5 CTanδ00000000000000 0
HV-SBR 0.149T-3335 0.130E-60 0.124E-50 0.115T-3330 0.114
Note:
Tanδ curve of E-50 &・ E-60 are sharp High Tanδ peak( ) → suggest good filler dispersion
Above room temp,・ Tanδ of E-50 & E-60 and T3330, 3335 lower than commercial HV-SBR. → good LRR properties expected.
Page 18
Asahi-SBR/BR blends vs #1712(same Tg) in silica
40
60
80
100
120
140
160
Bo
un
d r
ub
ber
Co
mp
d.
Mo
on
ey10
0°C
Hs(
Sh
oe-
A)
M30
0%
M30
0/M
100
Ten
sile
str
eng
th
Elo
gat
ion
Reb
ou
nd
50 ℃
G' 0
°C
0.1%
Tan
δ0°
C
0.1%
Tan
δ0°
C
3%
Tan
δ50
°C
3%
ΔT
anδ
50
°C
Ind
ex (
Lar
ge
valu
e p
refe
rab
le)
3330/U150=75/25
E-50/U150=65/35
SBR1712
August. 2001
Index=196
Advantages of Tufdene/BR blend in silica 1) Increased bound rubber and good filler dispersion (small Δ G') 2) Increased bound rubber
2) Higher M300%
3) Soft in lower temp
4) Goog low rolling resistance
Page 19
Wet grip(Tanδ @ C) vs RR(Tanδ @5 C) of0 0000 00 00 00 00 00 00 00 00 00 00 00 0 0 0E-50/BR blend in silica Compound
0.12
0.14
0.16
0.18
0.200.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Tanδ @ C(0.1% strain)00000000000000 0
Tan
δ5
C,3
% st
rain
00000000000000
0
T3330/BR
SBR1712
T3335/ BR
E-50/BR
65/35
85/15
65/35
75/25
100/0
100/0
100/0
Good
Compound recipeSBR+BR 100A-oil 37.5Silica 63N234 7Si69 5
August. 2001
Note :
LRR/wet grip balance・
E-50/BR blend
> T-3330/BR blend
> T-3335/BR blend
>= SBR 1712 Modefication and・ high Mol. wt make good effects on LRR in SBR/BR blend
Page 20
Wet grip(Tanδ @ C) vs Low temp Hardness(G'@ C) of0 0000 00 00 00 00 00 00 00 00 00 00 00 0 0 0E-50/BR blend in silica Compound
4
6
8
10
12
14
16
180.1 0.2 0.3 0.4 0.5 0.6 0.7
Tanδ @ C(0.1% strain)00000000000000 0
G' @
C,3
% st
rain
(MPa)
00000000000000
0
T3330/BR
SBR1712T3335/ BR
E-50/BR
65/35
85/15
65/35
75/25
100/0
100/0
100/0
Good
Compound recipeSBR+BR 100A-oil 37.5Silica 63N234 7Si69 5
August. 2001
Note :
Low temp hardness・ /wet grip balance
E-50/BR blend
> T-3330/BR blend >= T-3335/BR blend
> SBR 1712 Modefication and・
make good effects on Low temp. prop. in SBR/BR blend
Page 21
A u g u s t . 2 0 0 1 , A s a h i - K A S E I C o r p o r a t i o n
I n t r o d u c t i o n o f E - 1 0 , M o d i f i e d S B R f o r s i l i c a c o m p o u n d s
1 . O b j e c t o f d e v e l o p m e n t
D r y S B R ( N o n O E ) f o r S i l i c a c o m p o u n d w i t h s u p e r b a l a n c e d R R a n d G r i p p r o p e r t i e s
2 . C h a r a c t e r i s t i c s o f P o l y m e r s t r u c t u r e
a . N a r r o w M w / M n b y S o l u t i o n S B R t e c h n o l o g y b . T h e r e t y p e s o f C h e m i c a l m o d i f i c a t i o n s u i t a b l e f o r S i l i c a f i l e r c . H i g h T g ( - 2 8 ° C ) w i t h r a t h e r h i g h s t y r e n e c o n t e n t ( 3 9 w t % ) a n d m e d i u m v i n y l c o n t e n t ( 3 1 % i n B D )
3 . P e r f o r m a n c e i n s i l i c a c o m p o u n d s
a . A s a h i ' s c h e m i c a l m o d i f i c a t i o n f o r s i l i c a e x h i b i t s v e r y l o w T a n δ v a l u e a t a r o u n d 5 0 ° C . T a n δ a t 5 0 ° C o f E - 1 0 i n l o w o i l s i l i c a r e c i p e i s b e t t e r t h a n t h a t o f c o m m e r c i a l m o d i f i e d S - S B R .
b . H i g h T a n δ v a l u e a t l o w t e m p e r a t u r e ( a r o u n d 0 ° C ) i s a c h i e v e d b y h i g h T g s t r u c t u r e , b u t G ' v a l u e i s n o t s o l a r g e c o m p a r e d w i t h c o m m e r c i a l S - S B R w i t h m o d i f i c a t i o n .
c . S t r a i n d e p e n d e n c e o f T a n δ a n d G ' a r e v e r y s m a l l a n d P a y n e e f f e c t i s v e r y l o w i n t h e s i l i c a c o m p o u n d o f t h i s S B R b y i m p r o v e d s i l i c a d i s p e r s i o n .
4 . A p p l i c a t i o n
A s a h i t h i n k s t h i s S B R w o u l d m a k e s u p e r s i l i c a c o m p o u n d w i t h g o o d R R - G r i p b a l a n c e , a n d w o u l d b e s u i t a b l e f o r t i r e t r e a d c o m p o u n d w i t h l o w o i l r e c i p e o r e n v i r o n m e n t a l s a f e t y o i l r e c i p e .
P a g e 2 2
Table 1 Basic polymer structures of E-10
E-10 Modified SBR
Production scale Plant Plant
Oil content (phr) 0 0
Polymer Mooney Vis.(ML 1+4, 100°C) 72 45
Styrene content (wt%) 39 22
Vinyl content (% in BD) 31 65
Tg (°C, DSC mid) -28 -26
Remark Newly developed
Page 23
August. 2001
Fig . E-10 vs Commercila modified S-SBR
60
70
80
90
100
110
120
130
140
150
160B
ou
nd
Ru
bb
er
Co
mp
d.
M.
Vis
.
M3
00
%
M3
00
/M1
00
Te
ns
ile
str
en
gth
Elo
ng
ati
on
(%
)
Re
b.
@7
0°C
G'@
0°C
0.1
%
Ta
nδ
@0
°C
0.1
%
Ta
nδ
@0
°C,
3%
Ta
nδ
@5
0°C
, 3
%
ΔG
' @5
0°C
Ind
ex
(L
arg
e i
s p
refe
rab
le)
E-10
Commercail SSBR
August. 2001
Advatages of E-10
1)Higher Styrene MV-SBR with Fuctinal Group. 2) Good mechanical Properties(M300,Tb)
3) High hysterisis loss at low temp. → High grip
4) Low hysterisis loss at high temp. → Lower RR
5) Small Payne effect & large bound rubber → Good fiiler dispersion
Page 24
Fig. E-10 in Silica compound-Tanδ temperature dependence cureve
0.00
0.50
1.00
1.50
-40 -30 -20 -10 0 10 20 30 40 50 60 70
Temp.(℃)
tanδ
1
10
100
1000
G'(
MP
a)
E-10
Commercailmodified SBR
August. 2001
Commercailmodified SBR
E-10
Note : 1) High Tanδ peak 2) Lower Tanδ at high temperature 3) Lo wer G ' v al u e above C00000000000000 0
Page 25
Possibility to redudce Si69 content using E-50
60
80
100
120
140
160
180 B
ound
rub
ber
Com
pd. M
L (1
00℃
)
T-9
0%
M30
0%
Ten
sile
Str
engt
h
Elon
gation
G'
@ 0℃
0.1
%
δ @
0℃ 0
.1%
tan
δ @
0℃ 3
%ta
n
Reb
ound
5
C00000000000000
0
δ @
50℃
3%
tan
ΔG
' @5
C00000000000000
0
Inde
x(La
rge
valu
e is
pre
fera
ble)
14 C/Si69=6.3phr22222222222222 216 C/Si69=6.3phr00000000000000 0
16 C/Si69=3.15phr00000000000000 0
16 C/Si69=2.1phr00000000000000 0
August 2001
Possibilities to reduce Si69 content
1) Highe Mixing temp. improves LRR and wet grip properties. using E-50
2) Reduced Si69 content (Sulfur compensate) impreves silica disperdion
3) In both cases, increase of compound viscosity and danger to scorch are uneasy matter.
4) There would be a possibility to mix at higher temp. and reduced silane using stable coupling agent Si75.
Page 26
Good Copy
SummarySummary• Asahi’s MV-SBR : TT--3330 & T33353330 & T3335 (OE-SBR)
with good St/Vi balance , & Small modification→ Good results in EU & JP for silica tire.(LRR/Grip balance, Low temp. property, Wear Resistance.)
• New Grade EE--50 and E50 and E--6060 (OE-SBR) with Super Modification and Higher MwSuper Modification and Higher Mw
→ Improved LRR/Grip & Low temp/Grip balanceImproved LRR/Grip & Low temp/Grip balancewould be expected for silica tire in next stage
→ Possibility to reduce silanePossibility to reduce silane coupling agent
• New Grade EE--1010 (Dry-SBR)with Super ModificationSuper Modification
→ Application for low oil formulation & environmental safelow oil formulation & environmental safeoil formulationoil formulation would be expected.
Page 27August 2001
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