Polymerization of rigid rodlike molecules with reactive end groups requires near parallel orientation of the molecules. The reaction is diffusion limited because of the low mobility of the molecules in the later stages of the reaction. Experimental studies have shown that flow-induced molecular orientation enhances the rate of polymerization [Agarwal and Khakhar, Nature 360, 53 (1992)]. Here a theoretical study of the polymerization under axisymmetric extensional flow is carried out to obtain the effective reaction rate constant (keff) for the reaction. Computations show that an increase in the intrinsic rate constant (kh) results in a decrease in the relative rate constant krel=keff/kh. Reduction in the rotational diffusivity (Dr) results in a significant reduction in krel; however, the variation of the translational diffusion coefficient perpendicular to the rod axis D has only a small effect for D/D≪1, where D is the diffusivity parallel to the rod axis. The imposition of flow increases the effective rate constant, however, the variation of krel with other parameters remains qualitatively similar at different Peclet numbers (Pe=ε/Dr, where ε is the extensional rate). To simulate the variation of the rate constant during polymerization, computations are carried out for different rod lengths using correlations to estimate rod diffusivities. Results indicate that krel initially decreases and then increases after a certain critical degree of polymerization, which reduces with increase in Peclet number. For sufficiently high extensional rates (ε∼200s−1) the rate constant becomes higher than the intrinsic value (krel>1).

1.
J. E.
McIntyre
,
Macromolecules
22
,
4076
(
1989
).
2.
D. B.
Cotts
and
G. C.
Berry
,
Macromolecules
14
,
930
(
1981
).
3.
T. I.
Bair
,
P. W.
Morgan
, and
F. L.
Killian
,
Macromolecules
10
,
1396
(
1977
).
4.
J.
Bao
,
A.
You
,
S.
Zhang
, and
C.
Hu
,
J. Appl. Polym. Sci.
26
,
1211
(
1981
).
5.
P. R.
Dvornic
,
S. D.
Vignevic
, and
M. N.
Govedarica
,
J. Serb. Chem. Soc.
58
,
357
(
1993
).
6.
J. S. Gupta, A. Agge, and D. V. Khakhar, AIChE J. (accepted for publication, 2000).
7.
L. Volbracht, Comprehensive Polymer Science (Pergamon, Oxford, 1989), pp. 375–386.
8.
U. S.
Agarwal
and
D. W.
Khakhar
,
Nature (London)
360
,
53
(
1992
).
9.
U. S.
Agarwal
and
D. W.
Khakhar
,
Macromolecules
26
,
3960
(
1993
).
10.
B. W.
Jo
,
S. K.
Choi
,
J. K.
Choi
,
J. S.
Kim
,
J. H.
Chang
, and
J. I.
Jin
,
Polym. J. (Tokyo)
29
,
245
(
1997
).
11.
S. A. Rice, in Comprehensive Chemical Kinetics, Vol. 25, edited by C. H. Bamford, C. F. Tipper, and R. G. Compton (Elsevier, Amsterdam, 1985).
12.
I.
Mita
and
K.
Horie
,
J. Macromol. Sci. Rev. Macromol. Chem. C
27
,
91
(
1987
).
13.
Y. T.
Wu
and
J. M.
Nitsche
,
Chem. Eng. Sci.
50
,
1467
(
1995
).
14.
J. A.
McCammon
,
Curr. Opin. Struct. Biol.
8
,
245
(
1998
).
15.
D. V. Khakhar, in Molecular Dynamics from Classical to Quantum Methods, edited by P. B. Balbuena and J. M. Seminario (Elsevier, 1999), pp. 785–828.
16.
U. S.
Agarwal
and
D. V.
Khakhar
,
J. Chem. Phys.
96
,
7125
(
1992
).
17.
U. S.
Agarwal
and
D. V.
Khakhar
,
J. Chem. Phys.
99
,
1382
(
1993
).
18.
M. v.
Smoluchowski
,
Z. Phys. Chem., Stoechiom. Verwandtschaftsl.
92
,
129
(
1917
).
19.
J. S.
Gupta
and
D. V.
Khakhar
,
J. Chem. Phys.
108
,
5626
(
1998
).
20.
U. S.
Agarwal
and
D. V.
Khakhar
,
J. Chem. Phys.
99
,
3067
(
1993
).
21.
M. Doi and S. F. Edwards, The Theory of Polymer Dynamics (Oxford University, New York, 1986), pp. 330–420.
22.
M.
Doi
and
S. F.
Edwards
,
J. Chem. Soc., Faraday Trans.
74
,
560
(
1978
).
23.
S.
Broersma
,
J. Chem. Phys.
74
,
6989
(
1981
).
24.
I.
Teraoka
and
R. J.
Hayakawa
,
J. Chem. Phys.
89
,
6989
(
1988
).
25.
I.
Teraoka
and
R. J.
Hayakawa
,
J. Chem. Phys.
91
,
2643
(
1989
).
26.
W. H. Press, S. A. Teukolsky, W. T. Vellering, and B. P. Flannery, Numerical Recipes in C (Cambridge University Press, Cambridge, 1997), pp. 71–89.
27.
Sumeet Jain, Polymerization of Rigid Rodlike Molecules: Computations (B. Tech. Project, IIT Bombay, 2000), pp. 45–59.
28.
J. S. Gupta, Ph.D. thesis, IIT Bombay, 1997.
29.
J. M.
Whitcombe
,
C.
Alexander
, and
E. N.
Vulfson
,
SYNLETT
,
911
(
2000
).
30.
J. M.
Thomas
,
R.
Raja
,
G.
Sankar
, and
R. G.
Bell
,
Nature (London)
398
,
227
(
1999
).
This content is only available via PDF.
You do not currently have access to this content.