Effect of DPG on Silanization Chemistry

of Silica in Rubber Processing

Bound rubber study of silica
S. Mihara*1), R.N. Datta2), A.G. Talma2), W.K. Dierkes2)
and J.W.M Noordermeer2)

VKRT meeting on December 11

1) Yokohama Rubber Co., LTD 2-1 Oiwake, Hiratsuka, Kanagawa, Japan

2) University of Twente , Faculty of Engineering Technology,
Dept. of Elastomer Technology and Engineering
P.O. Box 217, 7500 AE Enschede , the Netherlands
1
1. Introduction
H H
N N
C
NH

1,3-diphenylguanidine (DPG)

ØSecondary cure accelerator in silica-filled rubber

ØInteraction with silica surface
ØToxic concerns
ØNegative influence on metal-rubber adhesion

2
1. Introduction
Crosslinking reaction

Sy
Polymer Sz

Silane-Rubber + Other reactions

Sx coupling Sx Sx H
N
H
N
TESPT (CH2)3 (CH2)3 (CH2)3 C
NH
H5C2O Si OC2H5 H5C2O Si O Si OC2H5
O OH O O
OH OH

Silanization Silica

Typical reactions during rubber processing

How does DPG influence on these reactions ???

3
Objectives
Understanding
1. Influence of DPG on silane chemistry

2. Role of DPG during rubber processing

1. Silanization kinetics
2. Crosslinking reaction between model olefins
3. Change of sulfur distribution in TESPT
4. TESPT-model olefin reaction
5. DPG-TESPT reaction

4
 2. Experimental
Materials

n-decane 2,3-dimethyl-2-butene
(TME)

Mixture 1 Mixture 2 Mixture 3 Mixture 4

n-decane 1.4600 1.4600 - -

2,3-dimethyl-2-butene - - 0.4000 0.4000
Silica 0.2000 0.2000
TESPT 0.0200 0.0200 0.0320 0.0320
DPG - 0.0040 - 0.0071 (g)

Silanization kinetics Crosslinking between model olefins

TESPT reaction with polymer or DPG
N-decane: (Aldrich) ; 2,3-dimehyl-2-butene: (Aldrich) ; 3-methyl-1-pentene: (Aldrich)
Silica: Zeosil 1165MP (Rhodia Silices) ; TESPT: Si69 (Degussa)
DPG: Perkacit DPG (Flexsys B.V) 5
Sample preparations
Reaction Mixtures Reaction Mixtures
Model olefin
TESPT Dip into oil bath at specified temperature
DPG
Silica
Cool down the reaction mixture with ice
N2 flow
Melt
Diethyleneglycol-monobutylether
treatment

Filtration of reaction mixture using micro pore filter

HPLC HPLC and MS

1. Silanization kinetics 2. Cross-linking products
3. TESPT-model olefin complex
4. TESPT-DPG complex 6
 Chromatographic and MS Conditions
HPLC conditions

Column Nucleosil 100-5 C18 HD

Length of column 250 mm S4

Intensity
Internal diameter 4.6 mm S3
Mobile phase Acetonitrile : water = 97 : 3 S2 S5
Flow rate 0.3 ml/min S6 S7
Temperature 23 C
Detector UV (DAD)
Retention time
Wavelength 254 nm (200 to 700 nm)
Injection volume 0.5 ml Chromatogram of TESPT (Mixture 1 or 2)
x105

MS ionization conditions in APCI 2.0 [ M + H] + 323.0

Intensity [mAU]
Flow rate 20 ml/min 1.5 266.9
294.9
Nebliser gas pressure 25 psi 1.0
Dry gas flow 3 L/min
0.5 238.9
Dry gas Temp. 320 C
Vaporise Temp. 425 C 0

250 300 350

APCI : Atmospheric Pressure Chemical Ionization Mass to charge ratio m/z
[ M + H] + is detected. 7
Calculation of kinetic parameters
S4
S3
S2 S5

C ( t 0 ) − C ( t1 )
S6 S7
x=
C( t0 ) Summed peak = amount of un-reacted TESPT

ln( 1 − x t1 ) − ln( 1 − x t0 )
k1 = [min −1 ]
t1 − t 0
x is conversion of TESPT, C(t0) and C(t1) are the amounts of un-reacted TESPT
at time t0 and t1, respectively, k1 is the rate constant of silanization.

Arrhenius equation Ea

ln k1
Ea
ln k1 = ln( k 0 ) −
RT
Ea is the activation energy, R is the gas constant, 1/T
T is the absolute temperature.
8
3.1 Influence of DPG on Silanization Kinetics
Conversion of TESPT
OC2H5 OC2H5
OH O Si (CH2)3
H5C2O Si (CH2)3 S2
+ S2
OH OC2H5
OC2H5
2 OH
Silica TESPT
0.0 0.0 0.0
without DPG without DPG without DPG
-1.0 -1.0 -1.0
ln(1-x)
ln(1-x)

ln(1-x)
-2.0 -2.0 -2.0
with DPG with DPG with DPG
-3.0 -3.0 -3.0 with
-4.0 (a) 120 C -4.0 (b) 140 C -4.0 (c) 160 C
-5.0 -5.0 -5.0
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
Time (min) Time (min) Time (min)

ØIn the presence of DPG conversion of TESPT

increases fast at the beginning of reaction.
9
3.1 Influence of DPG on Silanization Kinetics
Calculated kinetic parameters

Mixture 1 Mixture 2
without DPG with DPG

Rate constant k1 (1/min) 0.17 1.09

Activation energy Ea (kJ/mol) 29.3 11.0

Øk1 of increases by a factor of six.

ØEa decreases till one third.

DPG can accelerate the silanization reaction.

10
 3.2 Influence of DPG on crosslinking reaction
between model olefins
3
x10 S3** S4**
Intensity [mAU]

6.0 ** TESPT
S3* S4* S5**
4.0 S2**
2.0 S2* S5* S6*S6** S7**
0
18 20 22 24 26 28 Time [min]

DPG H3C CH3 H3C CH3

2 + Sx
Coming from TESPT H3C C Sx C CH3
H2 H2
Cross-linked product of TME
S.C. Debnath, R. N. Datta, J. W. M. Noordermeer, RUBBER CHEM. TECHNOL. 76, 1311 (2002).

11
3.2 Influence of DPG on crosslinking reaction
between model olefins
300000

250000
with DPG

Peak area [mAU]

200000

150000

100000 without DPG

50000
0
0 10 20 30 40
Reaction time (min)

ØThe total peak area of the cross-linked products increases with

increasing reaction time, even in the absence of elemental sulfur.
ØIn the presence of DPG the increase of the cross-linked products is
much faster compared to the DPG-free system.
TESPT acts as a sulfur donor during processing. 12
3.3 Influence of DPG on sulfur distribution in TESPT
OC2H5 OC2H5
H5C2O Si (CH2)3 Sx (CH2)3 Si OC2H5
OC2H5 OC2H5
*Reaction Temperature : 140 C
0.8 0.8
without DPG with DPG

Ratio of sulfur rank

Ratio of sulfur rank

0.6 0.6
S3
0.4 S3 0.4

0.2 0.2

0.0 0.0
0 10 20 30 40 0 10 20 30 40
Reaction time (min) Reaction time (min)
( ) : S2 ; ( ) : S3 ; ( ) : S4 ; ( ) : S5 ; ( ) : S6 ; ( ) : S7

In the presence of DPG the increase of the tri-sulfide is

relatively faster compared to the DPG-free system.
13
3.4 Influence of DPG on reaction between
TESPT and model olefins HC
CH
3
CH3

OC2H5 H3C CH3

S
+ H5C2O Si (CH2)3 Sx
OC2H5 2
H5C2O
Si
OC2H5
Extracted ion peak of 323 m/z OC2H5
5
( x 105)

46 [M + H+] = 323 m/z

( x 105)

5 34
3
4 2
( x 104)

55
Ion intensity x 104 ( mAU)

32 2

44 1
55 2 00 (d)
33 1 0 12 14 16 18 TME+TESPT+DPG (Mixture 4)
44 1 0 12 14 16 18
22
33 00 (c)
(b) TME+TESPT (Mixture 3)
1 1 00 12
12 14
14 16
16 18
18 Tim e [min]

22
0 (b) TME+DPG
11 00 12
12 14
14 16
16 18
18
00
0 12 14 16 18
(a) TME Reaction Temperature:140 ºC
0 12 14 16 18
Retention time (min)
Time: 30 minutes
14
3.4 Influence of DPG on reaction between
TESPT and model olefins
Fragmentation of 323 m/z using the MS
x105

2.0
[M + H+] 323.0
Intensity [mAU]

1.5
266.9
294.9
1.0

0.5
238.9
0

250 300 350

Mass to charge ratio

Masses of 295 m/z, 267 m/z and 239 m/z coming from
the TESPT-TME complex are obtained.
This decrease with each time 28 m/z can be related to progressive
hydrolysis of the ethoxy groups of the TESPT moiety.
15
3.4 Influence of DPG on reaction between
TESPT and model olefins
Possible structures of TESPT-Model Olefin Complex

H3C CH3 H3C CH3 H3C CH3 H3C CH3

CH CH CH CH
H3C CH3 CH3 CH3 CH3
S H3C S H3C S H3C S
- C2H4 - C2H4 - C2H4
Hydrolysis Hydrolysis Hydrolysis

H5C2O
Si
OC2H5 H5C2O Si OH H5C2O Si OH HO Si OH
OC2H5 OC2H5 OH OH

M + H+ = 323 M + H+ = 295 M + H+ = 267 M + H+ = 239

-28 m/z -28 m/z -28 m/z

16
3.4 Influence of DPG on reaction between
TESPT and model olefins
Amount of TESPT-Model Olefin Complex
12000000

10000000
Peak area [mAU]

with DPG
8000000

6000000

4000000
without DPG
2000000

0
0 10 20 30 40
Reaction time (min)

ØThe total peak area of TESPT-Model olefin complex

increases with increasing reaction time.
ØDPG is capable of accelerating the TESPT-model olefin reaction.
17
3.5 Reaction of TESPT with DPG
Extracted ion chromatograms of 530 m/z
5

5
4
x 105 [mAU]

Reaction Temperature:140 ºC
4 3 Time: 30 minutes

3 2

2 1
Intensity

(b) TME + TESPT + DPG

0
1
0 14 16 (Mixture 4)
0 (a) TME + TESPT (Mixture 3)
0 14 16
Retention time [min]

In the presence of DPG and TESPT

an extracted ion peak of 530 m/z can be seen.
18
 3.5 Reaction of TESPT with DPG

Fragments of TESPT – DPG complex due to elimination of sulfur

Intensity [mAU]

x 102 (a) x 102 (b) x 102

(c)
2 530 -32 498.5 -32 466
1.2
1 1
1.0
0
528 530 532 496 498 500 464 466 454
Mass to charge ratio (m/z) Mass to charge ratio (m/z) Mass to charge ratio (m/z)
H N
N
A decrease with 32 m/z each is observed,
Sx corresponding to elimination of sulfur
atoms from DPG-TESPT complex
(a) X=4 Mw = 530 m/z
H5C2O
Si (b) X=3 Mw = 498 m/z
OC2H5
H5C2O (c) X=2 Mw = 466 m/z 19
3.5 Reaction of TESPT with DPG

18

16

Peak area x 106 [mAU] 14

12
10

8
6

4
Mw=530 g/mol
2
0
0 10 20 30 40
Reaction time (min)

The total peak area of the DPG-TESPT complex slowly increases at the
beginning of the reaction and then increases very fast.

20
4. Conclusions
Due to the presence of DPG in reaction mixture…

1. The silanization reaction is promoted:

> Reaction Rate Constant of TESPT : Increasing by a factor of six

> Activation Energy : Decreasing till one third
2. The tri-sulfide isomer in TESPT increases.
> This tri-sulfide can possibly act as a sulfur donor during processing.
3. The amount of cross-linked products increases.

4. TESPT can itself react with the model olefin or DPG.

Therefore, significant amounts of DPG could be consumed

during processing due to this mutual TESPT-DPG reaction.
21
5. Acknowledgement
This project was financially supported by
YOKOHAMA RUBBER CO., LTD.

Thank you for your attention.

22