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Theoretical model of interfacial polymerization

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JOURNAL OF CHEMICAL PHYSICS VOLUME 121, NUMBER 22 8 DECEMBER 2004

Theoretical model of interfacial polymerization

Victor V. Yashina) and Anna C. Balazs
Department of Chemical and Petroleum Engineering, University of Pittsburgh,
Pittsburgh, Pennsylvania 15261
共Received 28 June 2004; accepted 16 September 2004兲
We present a theoretical description for the creation of a thin polymeric layer through the interfacial
polymerization of two immiscible, low molecular weight liquids. The theory specifically takes into
account the effects of polydispersity on the formation of the polymer film at the liquid-liquid
interface. Consequently, we can describe the structure of the growing film and the molecular weight
distribution of the resultant polymer chains. We focus on a model system where alternating AB
copolymers are formed at the interface between phase-separated, low molecular weight species A
and B. It is assumed that any A(B) unit can reversibly attach to any available B(A) unit or
B(A)-ended chain. The formation of the copolymer layer is described by a system of
reaction-diffusion equations, which detail the chemical evolution and diffusive dynamics of the
polydisperse mixture of AB copolymers around the interface, and the evolution of the interface
itself. Using this model, we determine the effects of the chemical reaction rates and the initial
conditions on the kinetics of forming the AB copolymer layer and the structure of this film.
© 2004 American Institute of Physics. 关DOI: 10.1063/1.1814354兴

I. INTRODUCTION tion of nonequilibrium processes in polydisperse mixtures is

Interfacial copolymerization takes place at an interface
of two immiscible, low molecular weight fluids, each con-
taining one of the reactants. The dissolved monomers diffuse
to the interface, where they undergo the copolymerization
reaction. The resulting copolymer is usually incompatible
with either of the liquid phases. As a result, a polymer film
grows at the interface 共see Refs. 1 and 2 and references
within兲. This technique is used to synthesize polyamides,
polyesters, polycarbonates, polyurethanes, and many other
macromolecules.1,2
Polymerization at liquid-liquid interfaces is also used to
form cell-like capsules that control the release of the encap-
sulated compound.2,3 In particular, interfacial polymerization
in oil/water emulsions is exploited to create drug-loaded cap-
sules of submicron size. These capsules form highly effective
carriers for drug delivery applications.3 Membrane technol-
ogy is another important application of interfacial polymer-
ization. The copolymerization reactions at the interface be-
tween an organic liquid and a porous support membrane,
which is impregnated with an aqueous solution, are widely
used for fabrication of thin-film composite membranes for
reverse osmosis and ultrafiltration.2,4
Besides their importance for technological applications,
studies of interfacial polymerization provide a greater under-
standing of structure formation in nonequilibrium systems
that involve both chemical reaction and phase separation. A
distinct feature of the systems that involve interfacial poly-
merization is polydispersity, i.e., the presence of components
with a broad distribution of size and mobility. The descrip-
a兲
Author to whom correspondence should be addressed. Electronic mail:
yashin@dorothy.che.pitt.edu
a challenging theoretical problem.
Recent developments in the theory of interfacial poly-
merization have mainly been inspired by the needs of tech-
nological applications in the areas of encapsulation5,6 and
membrane fabrication.4,7–9 The main goal of these studies
was to predict the kinetics of polymer film growth. A number
of assumptions were employed to formulate a mathematical
model. In particular, the growing polymer film was usually
described as a uniform layer and the reacting monomers
were assumed to diffuse towards a specific reaction zone.
The thickness of the polymer layer was obtained through the
material balance equations. Furthermore, the mobility of the
polymer chains was neglected, and evolution of the degree of
polymerization was not taken into account 共except in the
case of Ref. 7兲.
The uniformity of ultrathin membranes that are fabri-
cated through interfacial polymerization has been recently
questioned,9,10 and a theoretical model has been formulated
to describe the profile of the volume fraction of polymer
across the membrane. The neglect of the polymers’ mobility
is rationalized in this model by the fact that the monomers
form branched macromolecules.9
The main goal of the present study is to develop a theory
of interfacial polymerization that takes into account the ef-
fects of polydispersity on the formation of the polymer film
at the liquid-liquid interface. This model would allow us to
describe the structure of the growing film and the molecular
weight distribution 共MWD兲 of the resultant polymer chains.
In order to facilitate the development of a suitable theo-
retical approach, we considered a simplistic model of inter-
facial copolymerization. We consider the formation of a
strictly alternating AB copolymer at the interface of incom-
patible low molecular weight fluids A and B. It is assumed
that all monomers and all chain ends are reactive, and that

0021-9606/2004/121(22)/11440/15/$22.00 11440 © 2004 American Institute of Physics

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J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
FIG. 1. Schematic of the model of alternating copolymerization.
the growth of a polymer chain proceeds solely through the
addition of the monomers to the chain ends. The polymeriza-
tion reaction is assumed to be reversible; the irreversible re-
action is considered as a particular case. In Sec. II, the model
is described in detail; the equilibrium MWD is studied in the
case of a reversible polymerization reaction in a uniform
system and the choice of relevant variables is discussed. The
reaction-diffusion equations that describe the interfacial po-
lymerization in a phase-separating system are formulated in
Sec. III. In formulating the equations, the approach we de-
veloped in an earlier study11 is utilized to take into account
the effects of polydispersity. In Sec. IV, the derived reaction-
diffusion equations are applied to study interfacial polymer-
ization in a one-dimensional case, which corresponds to the
growth of a copolymer film at a planar interface. Our find-
ings are summarized in Sec. V.
II. MODEL
We consider the low molecular weight fluids A and B
that undergo phase separation. Simultaneous with the phase
separation, the A and B units react reversibly to form the
strictly alternating AB copolymer, which assumed to be in-
compatible with both A and B fluids. All the A and B mono-
mers and all the chain ends are assumed to be reactive. The
polymerization reaction is illustrated in Fig. 1. The rate con-
stants ␥ ⫹ and ␥ ⫺ of the forward and backward reactions,
respectively, are taken to be independent of the degree of
polymerization. The rate constant ␥ ⫹ of the forward reaction
is assumed to be sufficiently small to ensure that the reaction
is in the kinetically controlled regime. Although the polymer-
ization reaction studied here is reversible, the case of irre-
versible reaction can also be studied by taking the value for
the backward reaction rate constant to be zero. To simplify
the theoretical treatment, the reactive system is considered to
be incompressible. We consider a situation with no externally
imposed flows, and neglect hydrodynamic interactions. Thus,
reaction and diffusion are the only processes taken into ac-
count in the model.
A. Polymerization reaction
The model of polymerization shown schematically in
Fig. 1 is described by the following equations:
␥⫹
A⫹B↔ AB,
␥⫺
␥⫹
共 AB 兲 k ⫹A↔ 共 AB 兲 k A,
␥⫺
␥⫹
共 AB 兲 k ⫹B↔ B 共 AB 兲 k ,
␥⫺
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Theoretical model of interfacial polymerization 11441
␥⫹
共 AB 兲 k A⫹B↔ 共 AB 兲 k⫹1 , 共1d兲
␥⫺
␥⫹
B 共 AB 兲 k ⫹A↔ 共 AB 兲 k⫹1 , 共1e兲
␥⫺
where k⭓1 in Eqs. 共1b兲–共1e兲. The reacting system consists
of the monomers A and B, and of the chains of alternating
AB copolymers, which differ in their degree of polymeriza-
tion and in the type of end units. With respect to the two ends
of the chains, there are three populations of macromolecules
in the reacting system. In 关Eq. 共1兲兴, they are denoted as
(AB) k A, (AB) k , and B(AB) k , where k⭓1 is the number of
the AB pairs in a chain. The (AB) k A chains have the A units
at both of their ends, the (AB) k chains have one end unit of
the A type and another one of the B type, and, finally, the
B(AB) k chains have two B ends. We will refer to these three
types of the alternating copolymer as to the AA-, AB-, and
BB-ended chains, respectively. It is convenient to character-
ize the degree of polymerization of a polymer of type i
⫽AA, AB, or BB by the number k⭓1 of the AB pairs
within the chain.
We first consider the kinetics of the polymerization re-
action in a spatially homogeneous system. The results from
these calculations will provide a basis of comparison for the
more challenging case of polymerization in a spatially inho-
mogeneous system 共described in the following section兲. For
the case of the spatially homogeneous melt, the reaction ki-
netics is described by a set of rate equations for the concen-
trations of all species that may be present in the system in the
course of reaction. As is obvious from Eq. 共1兲, the complete
set of variables includes the concentrations C A and C B of the
monomers A and B, and the concentrations C AA AB
k , C k , and
BB
C k of the AA-, AB-, and BB-ended alternating copolymers,
respectively, which have k⭓1 AB pairs in chain. These con-
centrations depend on time t, however, for the convenience,
we do not explicitly write ‘‘C k (t)’’ in the ensuing equations.
It is convenient to make the concentration variables dimen-
sionless by means of multiplying them by the volume of a
monomeric unit v 0 , which is assumed to be equal for the A
and B units. Upon carrying out this procedure, the rate con-
stant of the forward reaction appears in the combination
␥ ⫹ v ⫺1
0 , for which the former notation ␥ ⫹ will be utilized for
brevity. Due to the incompressibility, the dimensionless con-
centrations C A and C B are the volume fractions of monomers
A and B, respectively, so the notations ␾ A and ␾ B will be
used instead. The rate equations describing the polymeriza-
tion reaction can readily be formulated in the following
共1a兲 form:
共1b兲 d␾A
dt
⫽⫺ ␥ ⫹ ␾ A ␾ B ⫺ ␥ ⫹ ␾ A 兺
k⫽1
k ⫹2C k 兲
共 C AB BB
共1c兲 ⫹␥⫺ 兺
k⫽1
k ⫹2C k 兲 ,
共 C AB AA
共2a兲
11442 J. Chem. Phys., Vol. 121, No. 22, 8 December 2004 V. V. Yashin and A. C. Balazs

d␾B
dt
⫽⫺ ␥ ⫹ ␾ A ␾ B ⫺ ␥ ⫹ ␾ B
k⫽1
兺 k ⫹2C k 兲
共 C AB AA

⫹␥⫺ 兺
k⫽1
k ⫹2C k 兲 ,
共 C AB BB
共2b兲

dC AB
1
⫽⫺ 关 ␥ ⫺ ⫹ ␥ ⫹ 共 ␾ A ⫹ ␾ B 兲兴 C AB
1 ⫹ ␥ ⫹␾ A␾ B
dt
⫹2 ␥ ⫺ 共 C AA
1 ⫹C 1 兲 ,
BB
共2c兲
k⭓2:
dC AB
k
⫽⫺ 关 2 ␥ ⫺ ⫹ ␥ ⫹ 共 ␾ A ⫹ ␾ B 兲兴 C AB
k ⫹2 ␥ ⫹ 共 ␾ A C k⫺1
BB
dt
⫹ ␾ B C k⫺1
AA
兲 ⫹2 ␥ ⫺ 共 C AA
k ⫹C k 兲 ,
BB
共2d兲
FIG. 2. The equilibrium weight MWD of the alternating AB copolymer
k⭓1: formed in the course of the polymerization reaction illustrated in Fig. 1 at
the ratio of the reaction rate constants of ␥ ⫹ / ␥ ⫺ ⫽100 under the equal and
dC AA
k unequal total contents of the A and B units in a spatially homogeneous
⫽⫺ 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ B 兲 C AA
k ⫹ ␥ ⫹ ␾ A C k ⫹ ␥ ⫺ C k⫹1 ,
AB AB
reacting system. A disparity in the A and B contents ( ␸ A ⫽0.5) leads to a
dt
共2e兲 formation of two distinct MWD curves corresponding to the chains with the
even and odd degrees of polymerization j.
dC BB
k
⫽⫺ 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ A 兲 C BB
k ⫹ ␥ ⫹ ␾ B C k ⫹ ␥ ⫺ C k⫹1 .
AB AB
dt
共2f兲 ␥⫺ k
k ⫽
C AB p , 共5b兲
␥⫹
It is seen that the rate equations 关Eqs. 共2a兲 and 共2b兲兴 for the
volume fractions of the A and B monomers are the same ␾B k
except for an interchange of A and B in the indices. A similar k ⫽
C BB p , 共5c兲
2
symmetry is observed for the rate equations 关Eqs. 共2e兲 and
共2f兲兴 for the concentrations of the AA- and BB-ended chains. where k⭓1 corresponds to the number of AB pairs in a
It is easy to check that Eq. 共2兲 conserves the total volume chain, and the parameter p is as follows:
fractions of A and B units ␸ A and ␸ B , respectively: p⫽ 共 ␥ ⫹ / ␥ ⫺ 兲 2 ␾ A ␾ B . 共6兲
d␸A d␸B The equilibrium values of the monomer volume fractions ␾ A
⫽ ⫽0. and ␾ B are determined from the system of two equations that
dt dt
include Eq. 共3兲 for the total volume fraction of A units ␸ A
The total volume fraction of A units is defined as and a similar equation for ␸ B ⫽1⫺ ␸ A . Then the polymer
volume fraction ␾ P is found as ␾ P ⫽1⫺ ␾ A ⫺ ␾ B . The
␸ A⫽ ␾ A⫹ 兺
k⫽1
k ⫹
共 k⫹1 兲 C AA 兺
k⫽1
k ⫹
kC AB 兺
k⫽1
kC BB
k . 共3兲 number-based and weight-based MWD of the polymer can
be found from Eq. 共5兲 using the standard definitions.1 It is
The value of ␸ B can be obtained through Eq. 共3兲 by inter- clear that the equilibrium polymer MWD is related to the
changing the A and B indices and the incompressibility con- Flory distribution since according to Eq. 共5兲
straint ␸ A ⫹ ␸ B ⫽1. The condition of incompressibility can
C ik ⫽C i 共 1⫺ p 兲 p k⫺1 , i⫽AA,AB,BB, 共7兲
also be represented as ␾ A ⫹ ␾ B ⫹ ␾ AA ⫹ ␾ AB ⫹ ␾ BB ⫽1,
where ␾ AA , ␾ AB , and ␾ BB are the volume fractions of the where C i is the concentration of all the chains of type i
AA-, AB-, and BB-ended macromolecules, respectively, de-
fined as shown below: C i⫽ 兺
k⫽1
C ik . 共8兲

␾ AA ⫽ 兺 共 2k⫹1 兲 C AA
k , ␾ AB ⫽2 兺 kC AB
k ,
The Flory number distribution is defined as n k ⫽(1
k⫽1 k⫽1 ⫺p)p k⫺1 , where n k is the number fraction of linear polymer
共4兲 chains with k⭓1 repeating units and p is the distribution
␾ BB ⫽ 兺 共 2k⫹1 兲 C BB
k . parameter.1
k⫽1
The polymerization equilibrium in a spatially homoge-
If the polymerization reaction is reversible ( ␥ ⫺ ⫽0) then neous system with the reaction described by Eq. 共1兲 is con-
an equilibrium state exists in the system. It is easy to show trolled by two parameters. These are the A/B composition of
that Eqs. 共2c兲–共2f兲 yield the following stationary solution: the system, which is characterized by the total volume frac-
tion of A units ␸ A and the ratio of the rate constants ␥ ⫹ / ␥ ⫺ .
␾A k Figure 2 shows the equilibrium weight MWD of the AB
k ⫽
C AA p , 共5a兲
2 copolymer at ␥ ⫹ / ␥ ⫺ ⫽100 for equal and slightly unequal

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J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
FIG. 3. Dependency of the equilibrium monomer content ␸ M ⫽ ␾ A ⫹ ␾ B on
the ratio of the reaction rate constants ␥ ⫹ / ␥ ⫺ at the total content of the A
units of ␸ A ⫽0.5 共solid curve兲 and 0.55 共dashed curve兲. At ␥ ⫹ / ␥ ⫺ ⬎100,
more than 95% of monomers are consumed by the polymerization reaction.
total A and B contents ( ␸ A ⫽0.5 and 0.55兲. The weight
MWD w j , where j⭓2 is the number of monomeric units in
a macromolecule, is calculated as
w j⫽ 再 AB
j C j/2 , even j
␾ P C 共AA
j⫺1 兲 /2⫹C 共 j⫺1 兲 /2 ,
BB
odd j.
As seen in Fig. 2, the equilibrium MWD points fall on a
single curve for all degrees of polymerization j if the total
content of the A and B units is equal ( ␸ A ⫽0.5). If, however,
there is a disparity in the total A and B content ( ␸ A ⫽0.55 in
Fig. 2兲, the equilibrium MWD is a combination of two dis-
tinct distributions, corresponding to the chains with even and
odd values of j. Obviously, an enrichment of the reacting
system with one type of the monomers, say with monomer A
as in Fig. 2, results in the preferential formation of polymers
with the chain-end units of that type (AA-ended chains in
this example兲.
At a given value of ␸ A , an increase in the ratio of the
reaction rate constants ( ␥ ⫹ / ␥ ⫺ ) leads to an increase in the
monomer-to-polymer conversion, and to the formation of
longer polymer chains, as shown in Figs. 3 and 4. The solid
lines in these figures correspond to ␸ A ⫽0.5 and the dashed
lines correspond to ␸ A ⫽0.55. Figure 3 shows the depen-
dence of the equilibrium monomer content ␸ M ⫽ ␾ A ⫹ ␾ B on
the value of ␥ ⫹ / ␥ ⫺ . Figure 4 presents the equilibrium
number-averaged degree of polymerization N̄ n 关Fig. 4共a兲兴
and the equilibrium polydispersity N̄ w /N̄ n 关Fig. 4共b兲兴 as
functions of ␥ ⫹ / ␥ ⫺ . In the latter case, N̄ w is the weight-
averaged degree of polymerization. As can be seen in Fig. 3,
the monomer content ␸ M in the reacting system drops
sharply with the increase in ␥ ⫹ / ␥ ⫺ from 0 to 100, at which
value more than 95% of the monomers are consumed by the
polymerization reaction. Figure 4共a兲 reveals that the polymer
chains formed in the course of the reaction defined by Eq. 共1兲
exhibit low equilibrium values of the degree of polymeriza-
tion; the equilibrium degree of polymerization N̄ n is just
about 24 at ␥ ⫹ / ␥ ⫺ ⫽500 and ␸ A ⫽0.5. As can be seen in
Fig. 4共b兲, the polydispersity N̄ w /N̄ n is about 1.9 at the latter
conditions. This value of the polydispersity is slightly lower
than that of a polymer with Flory’s molecular weight distri-
bution, for which N̄ w /N̄ n ⬇1.958 at N̄ n ⫽24. At ␸ A ⫽0.5, the
model predicts the formation of polymers with even lower
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Theoretical model of interfacial polymerization 11443
FIG. 4. Equilibrium number-averaged degree of polymerization 共a兲 and
polydispersity 共b兲 as functions of the ratio of the reaction rate constants
␥ ⫹ / ␥ ⫺ at the total content of the A units of ␸ A ⫽0.5 共solid curves兲 and 0.55
共dashed curves兲. The considered model of alternating copolymerization de-
scribes formation of short polymer chains.
molecular weights and narrower MWD, as illustrated in Fig.
3 by the results of calculations at ␸ A ⫽0.55 shown by the
dashed lines.
The low values for the equilibrium degree of polymer-
ization is a characteristic of this model and is a consequence
of the assumption that a polymer chain only grows due to the
reaction between the chain ends and monomers. Incorporat-
ing the reaction between chain ends into the model would
result in higher values of the degree of polymerization cal-
culated at equilibrium. It also is important to notice that the
system of rate equations 关Eq. 共2兲兴 implicitly assumes that the
reaction rate constants do not change in the course of reac-
tion. The latter might not be correct at high values of the
ratio ␥ ⫹ / ␥ ⫺ and low monomer contents because the forward
reaction steps might be controlled by the diffusive transport
of the reacting species at those conditions. The effects of this
diffusion-controlled behavior are systematically neglected in
this study.
B. Relevant variables
Having examined the polymerization reaction for our
system in a spatially homogeneous system, we now consider
the more complex scenario of a spatially inhomogeneous
chemically reacting system. In this case, the concentration
variables depend on both time t and the spatial position x,
and the diffusion processes should be taken into account. It is
unrealistic to describe the behavior of the reaction-diffusion
system in terms of the concentrations of all the possible spe-
cies. An enumeration of all these species would yield an
enormously high number because of the length polydisper-
sity exhibited by the product of the polymerization reaction.
In order to make a theoretical description feasible, some
11444 J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
small set of variables 兵 ␺ ␣ (x,t) 其 should be chosen to capture
the most important features of the system. 共We will refer to
these chosen variables as the relevant variables.兲 It is worth
noting that there is no general prescription for such a choice,
which is dictated merely by the physical and chemical nature
of the system under consideration, and by the desired level of
detail. Every choice of relevant variables is equivalent to a
certain approximation.
The strictly alternating structure of the macromolecules
and the incompatibility of the reacting components are the
main features of the model of interfacial polymerization un-
der consideration. We will use the following set of relevant
variables for the theoretical description of interfacial poly-
merization:
兵 ␺ ␣ 其 ⫽ 兵 ␾ A , ␾ AA ,C AA , ␾ AB ,C AB , ␾ BB ,C BB 其 .
The variables ␾ i and C i 共where i⫽AA, AB, or BB) are the
local concentrations and volume fractions of the polymer
chains of type i and are defined as in Eq. 共4兲 and Eq. 共8兲,
respectively, and ␾ A is the local volume fraction of the A
monomers. The concentration of polymer chains in a spa-
tially nonuniform system is defined as the concentration of
chain ends, with only one end of the polymer chain being
counted. When possible, the dependence of the variables
兵 ␺ ␣ 其 关Eq. 共9兲兴 on x and t is not displayed for the sake of
brevity. The use of the chain concentration variables C i al-
lows us to describe the formation of macromolecules with
strictly alternating sequences of A and B comonomers 关see
Eq. 共2兲兴. In turn, the morphology in the phase-separated, re-
acting system is described through the local volume fractions
of the reacting monomer and polymer species ␾ A and ␾ i ,
where i⫽AA, AB, or BB. Due to the incompressibility con-
dition, the volume fraction of the B monomers can be calcu-
lated as ␾ B ⫽1⫺ ␾ A ⫺ ␾ AA ⫺ ␾ AB ⫺ ␾ BB .
The choice of the relevant variables 兵 ␺ ␣ 其 关Eq. 共9兲兴 im-
plies an approximation to the local MWD of the polymeric
products of the polymerization reaction. Namely, the charac-
terization of polymer chains solely through their concentra-
tion and volume fraction is equivalent to the assumption that
the polymer MWD is described by the Flory distribution.11
The latter is discussed below in more detail.
III. THE REACTION-DIFFUSION EQUATIONS
In this section, we will formulate the equations to de-
scribe the simultaneous processes of the polymerization re-
action and diffusion 共phase separation proceeds through dif-
fusion兲 in terms of the chosen set of variables 兵 ␺ ␣ 其 关Eq. 共9兲兴.
Although as a whole, the mixture is a nonequilibrium sys-
tem, we assume that locally this system can be considered to
be at quasiequilibrium. The state of local equilibrium at the
position x and time t is specified by the relevant variables
兵 ␺ ␣ (x,t) 其 and characterized by a free energy density
f ( 兵 ␺ ␣ 其 ). The free energies of the local equilibrium regions
add up to the total free energy of the nonequilibrium system
F,
F⫽ 冕 dxf 共 兵 ␺ ␣ 其 兲 .
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V. V. Yashin and A. C. Balazs
Then, the reaction and interdiffusion processes are described
by the general equations of linear nonequilibrium thermody-
namics:
⳵␺␣ ជ
⳵t
⫽ⵜ 冉兺 ␤ ␦␺␤ 冊
ជ ␦ F ⫹R .
⌳ ␣␤ ⵜ ␣ 共11兲
The first term in the right-hand side 共rhs兲 of the above equa-
tion describes the interdiffusion of the system’s components
caused by the spatial nonhomogeneity of the chemical poten-
tials ␮ ␣ ⫽ ␦ F/ ␦ ␺ ␣ . According to the Onsager theorem, the
matrix of kinetic coefficients 储 ⌳ ␣␤ 储 共the Onsager kinetic co-
efficients兲 is symmetric: ⌳ ␣␤ ⫽⌳ ␤␣ . The second term in the
rhs of Eq. 共11兲 R ␣ describes the polymerization reaction.
Thus, we are to determine the free energy density f, the in-
共9兲 terdiffusion kinetic coefficients ⌳ ␣␤ , and the reaction con-
tribution R ␣ as functions of the relevant variables 兵 ␺ ␣ 其 . For
these purposes, we will utilize the approach we recently de-
veloped to study inderdiffusion in polydisperse polymer
blends.11
A. Free energy
The free energy density f of a polymer/monomer mixture
can be represented as a sum of three terms:
f ⫽ f mix ⫹ f con f ⫹ f int . 共12兲
The terms f mix and f con f are related to the mixing and con-
formational entropy, respectively, and f int is the contribution
from the energy of interaction between the components of
the mixture.
The term f mix in Eq. 共12兲 is the contribution from the
translational entropy, which describes the mixing of the vari-
ous species present in the mixture. The latter include the A
and B monomers and the polymers of type i, where i⫽AA,
AB, and BB, with k⭓1 AB pairs in a chain. Therefore, the
mixing entropy contribution to the free energy density is
given by the following equation:
⬁
f mix ⫽ ␾ A ln ␾ A ⫹ ␾ B ln ␾ B ⫹ 兺i k⫽1
兺 C ik ln C ik , 共13兲
provided that the MWD of each polymer component i, C ik , is
represented as a function solely of the relevant variables 关Eq.
共9兲兴. In order to construct such distributions 共relevant distri-
butions兲 in a thermodynamically consistent way, the proce-
dure of the maximization of the information entropy is
employed.11,12 The information entropy is defined as s in f
⫽⫺ f mix . According to this method,12 the information en-
tropy is to be maximized under the condition that for each
i⫽AA, AB, and BB, the desired MWD C ik provides the
values of the relevant variables ␾ i and C i defined by Eq. 共4兲
and Eq. 共8兲, respectively. By maximizing the entropy,
through the use of Lagrange multipliers, it becomes clear
that it is the Flory MWD that provides the relevant distribu-
tion for each component i⫽AA, AB, and BB,
C ik ⫽C i 共 1⫺ p i 兲 p k⫺1
i . 共14兲
The distribution parameter p i is defined in such a way that
共10兲
(1⫺ p i ) ⫺1 is the number-averaged mean number of the AB
pairs in the polymer of type i; this mean number is deter-
J. Chem. Phys., Vol. 121, No. 22, 8 December 2004 Theoretical model of interfacial polymerization 11445

mined through the relevant variables ␾ i and C i . The param-

eter p i , the variables ␾ i and C i , and the number-averaged F con f ⫽
1
2 兺i 冕␾ i 共 ⫺q 兲 ␾ i 共 q 兲
g i 共 q兲
dq. 共17兲
degree of polymerization N̄ i are related to each other as fol-
lows: In Eq. 共17兲, g i (q) is the equilibrium intrachain monomer-
monomer pair correlation function averaged with respect to
␾ i /C i ⫽N̄ i ⫽1⫹2 共 1⫺ p i 兲 ⫺1 , i⫽AA,BB, 共15a兲 the relevant MWD 关Eq. 共14兲兴:
⬁ 2k 共 ⫹1 兲
␾ AB /C AB ⫽N̄ AB ⫽2 共 1⫺ p AB 兲 ⫺1
. 共15b兲 g i共 q 兲 ⫽ 兺
k⫽1
C ik 兺
m,m ⬘ ⫽1
具 exp关 ⫺iq共 R̂m ⫺R̂m ⬘ 兲兴 典 0 .
As a result, the free energy of mixing f mix as a function of
Here R̂m is the radius vector of the mth monomer in a chain;
兵 ␺ ␣ 其 can be found from Eqs. 共13兲–共15兲: the ‘‘hat’’ sign over a symbol denotes a nonaveraged 共micro-
scopic兲 value. We assume that the chains are described by the
f mix ⫽ ␾ A ln ␾ A ⫹ ␾ B ln ␾ B ⫹ 兺i C i ln C i Gaussian model, in which case13,14
具 exp关 ⫺iq共 R̂m ⫺R̂m ⬘ 兲兴 典 0 ⫽exp共 ⫺a 2 q 2 兩 m⫺m ⬘ 兩 /6兲
Ci
⫹ 兺i 关 p ln p i ⫹ 共 1⫺ p i 兲 ln共 1⫺ p i 兲兴 .
1⫺p i i
共16兲 and a is a monomer size. Then, the correlation functions
g i (q) for i⫽AA, AB, and BB can easily be found as
The first three terms in the right-hand side of the above equa- 关 1⫹g 0 共 q 兲兴 2
tion describe intermixing of monomers A and B, and the g i 共 q 兲 ⫽C i ⫹2C i , i⫽AA,BB,
different types of polymers i⫽AA, AB, and BB. The last 共 1⫺ p i 兲关 1⫺ p i g 20 共 q 兲兴
term in the rhs of Eq. 共16兲 originates from polydispersity, and
关 1⫹g 0 共 q 兲兴关 1⫹ p AB g 0 共 q 兲兴
describes the intermixing of polymer chains of different g AB 共 q 兲 ⫽2C AB ,
length within the fractions of the AA-, AB-, and BB-ended 共 1⫺ p AB 兲关 1⫺ p AB g 20 共 q 兲兴
macromolecules. where g 0 (q)⫽exp(⫺a2q2/6). Finally, the q 2 terms, obtained
The term f con f in Eq. 共12兲 describes the loss of the con- from expanding g ⫺1
i (q) in Eq. 共17兲, provide the desired con-
formational entropy of polymer chains due to nonuniformi- formational entropy contribution to the density of free en-
ties over a length scale that is less than the radius of a poly- ergy:
mer coil. This contribution to the free energy density is
a2
兺i K i共 ⵜជ ␾ i 兲 2 .
essential in incompatible mixtures containing polymers since
f con f ⫽ 共18兲
f con f affects the interfacial tension in the phase-separated 6
system. The conformational entropy contribution can be ob-
tained through the random phase approximation 共RPA兲 ap- In the above equation, the coefficient functions K i , with i
ជ ␺ . 13,14 We ⫽AA, AB, and BB, have the following form:
proach as a gradient expansion in terms of ⵜ ␣
assume that the nonuniformities are rather smooth. There- 8 共 1⫹ p i 兲共 3⫺ p i 兲
fore, only the first terms of the expansion, which are qua- K i⫽ , i⫽AA,BB, 共19a兲
dratic with respect to ⵜ ជ ␺ , will be taken into account. ␾ i 关 8⫹ 共 1⫺ p i 兲 2 兴 2
␣
As noted above, polymers of type i, where i⫽AA, AB, 1⫹6p AB ⫹ p AB
2
or BB, are described by the local volume fraction ␾ i and K AB ⫽ . 共19b兲
concentration of chain ends C i . It might be anticipated that 4 ␾ AB 共 1⫹ p AB 兲 2
the conformational entropy term includes both ⵜ ជ ␾ and
i The limiting case of long polymer chains corresponds to p i
ជ
ⵜ C i . However, it has been shown that the chain ends follow →1 in Eq. 共19兲, which gives K i ⫽(2 ␾ i ) ⫺1 . It is worth not-
the local variations of the composition ␾ i in such a way that ing that this value of the coefficient K i is three times greater
their contribution can be neglected from f con f . 11 Thus, the than that of the coefficient obtained in the case of long mono-
gradient corrections proportional to (ⵜ ជ ␾ ) 2 can be obtained disperse polymers; that is, K i ⫽(6 ␾ i ) ⫺1 . 13
i
using the customary RPA formulation, which deals only with The last term in Eq. 共12兲 describes interactions between
the chain volume fractions.13 dissimilar species, i.e., the A and B monomers, and the mo-
Let us consider a locally equilibrated part 共cell兲 of the nomeric units belonging to the polymer chains. The custom-
system in which the volume fraction of polymers of type i ary approach to describe interactions in polymer systems em-
experiences certain variation ␦ ␾ i (x) around the local aver- ploys the mean-field approximation through the introduction
age value ␾ i ; that is, ␾ i (x)⫽ ␾ i ⫹ ␦ ␾ i (x). We assume that of the binary Flory-Huggins terms:13,14
兰 ␦ ␾ i (x)dx⫽0 where the integration is performed over of
f int ⫽ ␹ AB ␾ A ␾ B ⫹ ␹ A P ␾ A ␾ P ⫹ ␹ B P ␾ B ␾ P . 共20兲
the cell volume. Instead of the variation ␦ ␾ i (x), it is conve-
nient to operate with its Fourier amplitude ␾ i (q), which van- As before, ␾ P ⫽1⫺ ␾ A ⫺ ␾ B is the volume fraction of the
ishes in the limit of zero wave vector q→0. If the variations polymers in the system. If the system undergoes a phase
of ␾ i (q) can be regarded as small, then their effect can be separation, the rhs of Eq. 共20兲 should be expanded to include
described by a quadratic correction to free energy. The RPA the gradient corrections that originate from the nonunifor-
approach provides the following equation for this mity of the mixture’s composition on the length scale of the
correction:13 radius of particle-particle interactions.15–17 These gradient

Downloaded 30 Nov 2004 to 136.142.88.132. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
11446 J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
terms are essential for the theory of phase separation in sys-
tems of low molecular weight species as they provide the
means to describe the finite width of the interfaces. In poly-
mer blends, the gradient corrections to the Flory-Huggins
terms 关Eq. 共20兲兴 are usually not of significant importance
relative to the conformational entropy f con f 关Eq. 共18兲兴 be-
cause of the low values of the ␹ parameters that are charac-
teristic to phase separation in polymers.13,16 However, this
might not be the case in the system with interfacial polymer-
ization, in which the A and B monomers and the polymer are
mutually immiscible. Therefore, we add the corresponding
gradient corrections to the Flory-Huggins interaction energy
关Eq. 共20兲兴:
冋 册
l 20
f int ⫽ ␹ AB ␾ A ␾ B ⫺ ជ ␾ 兲共 ⵜ
共ⵜ ជ␾ 兲
A B
6 definition of the diffusion flux can be written as follows:11,12
冋
⫹ ␹ A P ␾ A␾ P⫺
l 20
6
ជ ␾ 兲共 ⵜ
共ⵜ A
ជ␾ 兲
P 册
冋 册
l 20
⫹ ␹ B P ␾ B␾ P⫺ ជ ␾ 兲共 ⵜ
共ⵜ ជ␾ 兲 .
B P
6
Here, l 0 is the characteristic interaction range, which is as-
sumed to be equal for all of the interactions. The interaction
contribution to the free energy density in the form of Eq. 共21兲
allows us to capture the finite interfacial width at any stage
of the reaction.
Thus, Eqs. 共16兲, 共18兲, and 共21兲 define the free energy
density f 关Eq. 共12兲兴 in terms of the relevant variables 兵 ␺ ␣ 其 .
The thermodynamic forces driving the diffusion processes
can now be found as ⫺ⵜ ជ ( ␦ F/ ␦ ␺ ). In following section,
␣
we will calculate the kinetic coefficients ⌳ ␣␤ , which multi-
ply the ⫺ⵜ ជ ( ␦ F/ ␦ ␺ ) term 关Eq. 共11兲兴.
␣
B. The Onsager kinetic coefficients
The kinetic coefficients ⌳ ␣␤ in Eq. 共11兲 are the coeffi-
cients in the linear relationship between the diffusion fluxes
and the thermodynamic forces driving the diffusion. The ki-
netic coefficients describe the contribution of the individual
monomers and chains to the collective diffusive motions in
the mixture. Consequently, the kinetic coefficients depend on
the mobility of every component in the mixture and the mix-
ture composition. To determine the matrix of kinetic coeffi-
cients ⌳⫽ 储 ⌳ ␣␤ 储 we will use the Green-Kubo equations.12
These equations establish a general connection between the
kinetic coefficient ⌳ ␣␤ and the equilibrium two-time corre-
lation functions of the properly defined microscopic diffu-
sion fluxes associated with the relevant variables ␺ ␣ and ␺ ␤ .
The Green-Kubo equations can be written as shown below,
⌳ ␣␤ 共 x,t 兲 ⫽
V
3
冕
0
⬁
d ␶ 具 ĵ共␣d 兲 共 ␶ 兲 •ĵ共␤d 兲 共 0 兲 典 共0x,t 兲 .
In Eq. 共22兲, ĵ␣(d) ( ␶ ) is the microscopic diffusion flux associ-
ated with the variable ␺ ␣ . The diffusion flux is averaged
over the volume V; the subscript d stands for ‘‘diffusion,’’
and the ‘‘hat’’ sign over a symbol denotes a microscopic
value. The evolution of the flux ĵ␣(d) ( ␶ ) with time ␶ is gov-
erned by the microscopic dynamics of the system. The two-
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V. V. Yashin and A. C. Balazs
time correlation function of the microscopic diffusion fluxes
is obtained by statistical averaging over a local-equilibrium
distribution function, whose parameters depend on x and t.
The angular brackets 具 ¯ 典 (x,t)
0 in Eq. 共22兲 denote this aver-
aging procedure with the subscript ‘‘0’’ standing for the local
equilibrium. A rigorous statistical mechanical calculation of
the flux correlation function in Eq. 共22兲 is a very difficult
task. It has been demonstrated, however, that under certain
approximations, the Green-Kubo equations can be used to
determine the dependence of the kinetic coefficient ⌳ ␣␤ on
the relevant variables 兵 ␺ ␣ 其 and on the mobility of the species
present in the mixture.11 In this section, we follow the ap-
proach of Ref. 11 to obtain the kinetic coefficients.
We consider the idealized case where the monomeric
units A and B have equal volume and equal mass. Then, the
ĵ共␣d 兲 ⫽ĵ␣ ⫺ ␺ ␣ Ĵ. 共23兲
In the above equation, ĵ␣ is the microscopic flux of all spe-
cies that contribute to the variable ␺ ␣ and Ĵ is the total
共21兲
microscopic flux. The flux ĵ␣ is determined through the ve-
locities v̂i ␣ of the contributing species:
ĵ␣ ⫽V ⫺1 兺
i
v̂i .
␣
␣
The set of microscopic fluxes 兵 ĵ␣ 其 ⫽ 兵 ĴA ,ĴAA ,ĵAA ,ĴAB ,
ĵAB ,ĴBB ,ĵBB 其 is defined in accordance with the set of
relevant variables 兵 ␺ ␣ 其 ⫽ 兵 ␾ A , ␾ AA ,C AA , ␾ AB ,C AB , ␾ BB ,
C BB 其 . Thus, ĴA is the flux of A monomers, whereas Ĵi and ĵi
共with i⫽AA, AB, and BB) are the respective fluxes of all
units of chains of type i and of their ends only; one end of
each chain is counted in ĵi . Correspondingly, the total flux Ĵ
is the sum of the all monomer and all polymer fluxes:
Ĵ⫽ 兺i Ĵi , i⫽A,B,AA,AB,BB.
The above diffusion fluxes 关Eq. 共23兲兴 are substituted into
the Green-Kubo equation 关Eq. 共22兲兴. The crucial approxima-
tion in calculating the flux correlation function is to neglect
the correlations in velocities of different moving objects in
the course of interdiffusion. Next, we restrict our consider-
ation to the rather large space and time scales where the
diffusive motions of a single polymer chain can be described
by the diffusion of its center of mass. Hence, the flux corre-
lation function 具 ĵ␣ ( ␶ )•ĵ␤ (0) 典 0 is represented by a sum of the
velocity correlation functions associated with the diffusive
motions of the individual monomers and polymer chains.
Each of the velocity autocorrelation functions contributes to
共22兲
⌳ ␣␤ through the corresponding self-diffusion coefficient D
in accordance with the well-know equation D⫽1/3兰 ⬁0 具 v̂( ␶ )
•v̂(0) 典 0 d ␶ . 18 We assume that the self-diffusion coefficient D
is inversely proportional to the number of monomeric units
N⭓1 in a diffusing object, and that the coefficient of pro-
portionality is equal for the monomers and polymers of all
types i⫽A, B, AA, AB, and BB. That is, D i (N)⫽D 0 N ⫺1 .
The latter equation implies that the polymer chains are un-
entangled, and that the effect of hydrodynamic interactions
J. Chem. Phys., Vol. 121, No. 22, 8 December 2004 Theoretical model of interfacial polymerization 11447

on the diffusion of polymer chains can be neglected. As
stated at the outset, it is assumed that the polymer chains
phase separate from the monomeric A and B liquids. The
hydrodynamic interactions are insignificant in the concen-
trated polymer phase.14
The flux correlation functions 具 ĵ␣ ( ␶ )•ĵ␤ (0) 典 0 with ␣,
␤⫽1,2,...,7 generate the following contributions to ⌳ ␣␤ 关Eq.
共22兲兴:
By definition 关Eq. 共26c兲兴, the matrix ⌳A,i is a 1⫻2 row ma-
trix.
The matrix of kinetic coefficients ⌳ accounts for the
polydispersity of the polymeric components of the mixture
through the presence of the factor N ⫺1 i in Eq. 共26b兲. At
⫺1 ⫺1
N i ⫽N̄ i , this factor leads to a contribution to the matrix
⌳ originating from the relative diffusion of polymers of the
same type i but with different numbers of monomers in the

冕 ⬁
chains, as discussed in Ref. 11.
V
d ␶ 具 Ĵi 共 ␶ 兲 •Ĵi 共 0 兲 典 0 ⫽D 0 ␾ i , i⫽A,B,AA,AB,BB, The free energy density f 关Eq. 共12兲兴 and the matrix of the
3 0 kinetic coefficients ⌳ 关Eq. 共25兲兴 provide the description of
共24a兲 the diffusion processes in the reaction-diffusion system that
V
3
冕
0
⬁
d ␶ 具 ĵi 共 ␶ 兲 •Ĵi 共 0 兲 典 0 ⫽D 0 C i , i⫽AA,AB,BB,
is characterized by the relevant variables 兵 ␺ ␣ 其 . We now go
on to specify the reaction term R ␣ in Eq. 共11兲.
共24b兲
V
3
冕
0
⬁
d ␶ 具 ĵi 共 ␶ 兲 •ĵi 共 0 兲 典 0 ⫽D 0 C i N ⫺1
i , i⫽AA,AB,BB.
C. Reaction terms
The reaction terms R ␣ in the rhs of Eq. 共11兲 are obtained
共24c兲 from the rate equations 关Eq. 共2兲兴 through the use of the defi-
nitions of the polymer volume fraction ␾ i and concentration
The average inverse degree of polymerization N ⫺1 present in
i C i given by Eq. 共4兲 and Eq. 共8兲, respectively. The relevant
Eq. 共24c兲 is calculated using the Flory MWD given by Eq.
MWD 关Eq. 共14兲兴 is utilized to obtain a closed system of
共14兲:
equations. The resulting reaction rate terms for the set of
1⫺p i relevant variables 兵 ␺ ␣ 其 are shown below:

冉 冊
N ⫺1
i ⫽ i 兲 ⫺p i 兴 ,
关 arctanh共 p 1/2 1/2
i⫽AA,BB,
p 3/2 ⳵␾A
i
⫽⫺ ␥ ⫹ ␾ A 共 ␾ B ⫹C AB ⫹2C BB 兲
⳵t react
⫺1
1⫺p AB
N AB ⫽ ln关共 1⫺ p AB 兲 ⫺1 兴 .
2p AB ⫹ ␥ ⫺ 共 C AB ⫹2C AA 兲 , 共27a兲
Finally, the resulting matrix of the kinetic coefficients
⌳⫽ 储 ⌳ ␣␤ 储 is obtained by combining the terms given by Eq. 冉 冊
⳵ ␾ AA
⳵t react
⫽⫺ 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ B 兲 ␾ AA
共24兲 as prescribed by the Green-Kubo equations 关Eq. 共22兲兴
and the definition of the diffusion flux 关Eq. 共23兲兴. The sym- ⫹ 共 ␥ ⫹ ␾ A ⫹ ␥ ⫺ p AB 兲共 C AB ⫹ ␾ AB 兲 , 共27b兲

冉 冊
metric 7⫻7 matrix ⌳ can be represented in the following
⳵ C AA

冉 冊
block form: ⫽⫺ 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ B 兲 C AA
⳵t react
⌳ A,A ⌳A,AA ⌳A,AB ⌳A,BB
⌳A,AA
T
⌳AA,AA ⌳AA,AB ⌳AA,BB ⫹ 共 ␥ ⫹ ␾ A ⫹ ␥ ⫺ p AB 兲 C AB , 共27c兲
⌳⫽
⌳A,AB
T

⌳A,BB
T
⌳AA,AB
T

⌳AA,BB
T
⌳AB,AB
⌳AB,BB
T
⌳AB,BB
⌳BB,BB
. 共25兲
冉 冊
⳵ ␾ AB
⳵t react
⫽2 ␥ ⫹ ␾ A ␾ B ⫹2 ␥ ⫺ 共 1⫺ p AB 兲 C AB

In the above equation, the superscript ‘‘T’’ denotes the ma- ⫺ ␾ AB 关 2 ␥ ⫺ ⫹ ␥ ⫹ 共 ␾ A ⫹ ␾ B 兲兴

trix transposition operation. The diagonal block elements of ⫹2 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ B 兲 ␾ AA ⫹2 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ A 兲 ␾ BB
the matrix of kinetic coefficients are found as shown below:
⫹2 共 ␥ ⫹ ␾ B ⫺ ␥ ⫺ 兲 C AA ⫹2 共 ␥ ⫹ ␾ A ⫺ ␥ ⫺ 兲 C BB ,
⌳ A,A ⫽D 0 ␾ A 共 1⫺ ␾ A 兲 , 共26a兲

冉 冊
共27d兲
␾ i 共 1⫺ ␾ i 兲 C i 共 1⫺ ␾ i 兲
⌳i,i ⫽D 0
C i 共 1⫺ ␾ i 兲 C i 共 N ⫺1
i ⫺C i 兲
,
冉 冊
⳵ C AB
⳵t react
⫽ ␥ ⫹ ␾ A ␾ B ⫹ ␥ ⫺ 共 1⫺ p AB 兲 C AB

i⫽AA,AB,BB. 共26b兲
⫺C AB 关 2 ␥ ⫺ ⫹ ␥ ⫹ 共 ␾ A ⫹ ␾ B 兲兴
The off-diagonal elements of the matrix ⌳ 关Eq. 共25兲兴 are as
⫹2 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ B 兲 C AA ⫹2 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ A 兲 C BB ,
follows:
共27e兲
⌳A,i ⫽⫺D 0 共 ␾ A ␾ i ␾ A C i 兲 , i⫽AA,AB,BB, 共26c兲

⌳i, j ⫽⫺D 0 冉 ␾ i␾ j ␾ iC j
冊 , i, j⫽AA,AB,BB, i⫽ j.
冉 冊
⳵ ␾ BB
⳵t react
⫽⫺ 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ A 兲 ␾ BB
C i␾ j C iC j
共26d兲 ⫹ 共 ␥ ⫹ ␾ B ⫹ ␥ ⫺ p AB 兲共 C AB ⫹ ␾ AB 兲 , 共27f兲

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11448 J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
冉 冊
⳵ C BB
⳵t react
⫽⫺ 共 ␥ ⫺ ⫹ ␥ ⫹ ␾ A 兲 C BB ⫹ 共 ␥ ⫹ ␾ B ⫹ ␥ ⫺ p AB 兲 C AB .
共27g兲
The parameter p AB is defined by Eq. 共15b兲, and appears in
the above equations due to the closure procedure. It is worth
noting that Eqs. 共27兲 are exact in the case of nonreversible
reactions; the parameter p AB is absent from Eqs. 共27兲 at ␥ ⫺
⫽0. If the reaction is reversible ( ␥ ⫺ ⫽0), then Eqs. 共27兲
yield the exact stationary solution 关Eq. 共5兲兴 in the case of
spatial homogeneity.
The reaction rate at a point x is determined by Eq. 共27兲
through only the local values of the variables 兵 ␺ ␣ (x) 其 . How-
ever, the local description of the polymerization reaction
might be insufficient in a system with rather sharp nonuni-
formities when the nonlocal character of the polymer chains
becomes apparent. We neglect such nonlocal effects in this
study.
Before proceeding to the application of the above model,
we make a few summarizing comments. It is clear from the
preceding sections that formulating the theoretical descrip-
tion of the length polydispersity is the main challenge in
deriving the reaction-diffusion equations for the interfacial
polymerization process. To solve this problem, we have
made an assumption that the set of variables 兵 ␺ ␣ 其 关Eq. 共9兲兴
provides an adequate, though approximate, description of the
reaction-diffusion processes in the system. The general
reaction-diffusion equations 关Eq. 共11兲兴 have been formulated
in terms of the relevant variables 兵 ␺ ␣ 其 utilizing the approach
presented in Ref. 11. According to this approach, the MWD
of each type of copolymer chain is approximated by the cor-
responding relevant distribution. These relevant distributions
are fully determined by the chosen set of the relevant vari-
ables 兵 ␺ ␣ 其 , and are obtained through the method of maximi-
zation of the information entropy known in statistical
mechanics.12 For the set of relevant variables 兵 ␺ ␣ 其 defined
by Eq. 共9兲, the relevant MWD is provided by the Flory dis-
tribution 关Eq. 共14兲兴. The distribution 关Eq. 共14兲兴 was then used
to determine the entropic contributions to the free energy
density f 关Eqs. 共16兲 and 共18兲兴, to calculate the Onsager ki-
netic coefficients ⌳ ␣␤ 关Eqs. 共24兲–共26兲兴, and to decouple the
equations of chemical kinetics 关Eq. 共2兲兴 in order to obtain the
reaction terms R ␣ 关Eq. 共27兲兴. As a result, the model of inter-
facial polymerization 关Eq. 共1兲兴 is described by the closed
system of reaction-diffusion equations for the relevant vari-
ables 兵 ␺ ␣ 其 关Eq. 共9兲兴. The obtained Onsager kinetic coeffi-
cients ⌳ ␣␤ 关Eqs. 共25兲 and 共26兲兴 correspond to the so-called
‘‘fast-mode’’ interdiffusion theory.11,19
The theoretical approach, which is employed in the
present paper to study a reacting polymer system with length
polydispersity, has been employed previously to model a re-
acting polymer blend that exhibits chemical polydispersity.20
Namely, a blend of two polymers has been considered, where
the pendant groups of one of the components undergo a
chemical reaction. The reaction depends on the type of the
neighboring units and results in the formation of a random
copolymer. In a nonhomogeneous blend, both the chemical
composition of a copolymer chain and the distribution of the
reacted and nonreacted units along the chain length depend
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V. V. Yashin and A. C. Balazs
on the location in space. The copolymer structure evolves
due to the simultaneous processes of interdiffusion and
chemical reaction.20,21 The chemical polydispersity was de-
scribed by including such characteristics of the random co-
polymer as the mean composition and the mean diadic con-
tent into the set of relevant variables. The resulting reaction-
diffusion equations were then derived following the same
steps as discussed in the above paragraph.20
It is worth noting that the reaction-diffusion equations
关Eq. 共11兲兴 allow a description of the morphology develop-
ment in a reacting polymer system with a macroscopically
nonuniform MWD. However, this is achieved at the cost of
loosing details of the MWD that are not captured by the set
of relative variables chosen. An alternative approach to de-
scribe the reacting polydisperse polymer system employs the
equations for the structure factors, as has been done in Ref.
22. Applicability of this approach is usually limited to de-
scribe slightly nonhomogeneous systems, in which the
MWD is macroscopically uniform. A spatially uniform
MWD can be determined in detail. The diffusion part of the
equations for the structure factors can be obtained by extend-
ing approaches that were developed to describe interdiffu-
sion in monodisperse binary blends to the case of a multi-
component system.22,23
Although the present paper concerns the nonequilibrium
behavior of the reacting polydisperse system, it is important
to note that significant progress has been made in studying
polydisperse systems at equilibrium using the so-called pro-
jection method.24 This method is used to calculate the static
coexistence curves for various polydisperse systems with an
a priori known distribution function characterizing the poly-
dipersity 共‘‘parent’’ distribution兲. Technically, the projection
method is almost identical to the derivation of the free en-
ergy density f in terms of the relevant variables as is done in
Refs. 11 and 20, and in the present paper. Namely, the chosen
moments of a distribution function serve as the relevant vari-
ables, and the entropy maximization procedure is utilized to
determine the ‘‘family’’ distribution—the analog of the rel-
evant distribution—which then is used to obtain the ‘‘pro-
jected’’ free energy as a function of the chosen moments.
However, the family distribution is scaled in such a way that
it is proportional to the parent distribution, and the family to
parent ratio depends only on the chosen moments 共see Ref.
24 for the further details兲. The projection method has been
used to demonstrate that the phase diagram of a polydisperse
system is very rich, and that a rather high number of the
moments have to be taken into account in order to obtain
accurate phase diagram.24 The projection method has limited
applicability in describing reacting systems because the poly-
dispersity evolves in time so the usefulness of the parent
distribution in formulating the reaction-diffusion equations is
questionable.
IV. RESULTS AND DISCUSSION: INTERFACIAL
POLYMERIZATION AT A PLANAR INTERFACE
In this section, we apply the approach developed above
to study interfacial polymerization in one dimension 共along
the x axis兲 for our system, which involves the formation of a
J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
layer AB copolymer at a planar interface between two im-
miscible, low molecular weight fluids A and B. The system is
described in terms of the set of chosen relevant variables
兵 ␺ ␣ 其 关Eq. 共9兲兴. As discussed in Secs. II B and III A, this
choice of variables is equivalent to approximating the MWD
of each type of copolymer chain by the Flory distribution
关Eq. 共14兲兴.
The evolution of the system is described by the reaction-
diffusion equations 关Eq. 共11兲兴. These equations are fully
specified by the free energy density f 关Eq. 共12兲兴, the matrix of
the kinetic coefficients ⌳ 关Eq. 共25兲兴, and the reaction rate
terms R ␣ 关Eq. 共27兲兴. The reaction-diffusion equations are
solved in the interval 0⭐x⭐L subject to the no-flux bound-
ary conditions at x⫽0, L:
⳵␺␣
⳵x
冏 x⫽0,L
⫽0. 共28兲
We assume that the initial system 共at t⫽0) does not contain
polymer chains
␾ i 共 x,0兲 ⫽C i 共 x,0兲 ⫽0, i⫽AA,AB,BB. 共29兲
The initial distribution of the monomers is taken to be of the
form of a sharp interface between the uniform A- and B-rich
phases:
␾ A 共 x,0兲 ⫽ 21 兵 1⫹ ␾ 0 tanh关 ␦ 0 共 x/L⫺1/2兲兴 其 ,
共30兲
␾ B 共 x,0兲 ⫽1⫺ ␾ A 共 x,0兲 .
The interface is located at x⫽L/2, and the parameter ␦ ⫺1
0
⬍1 gives the interfacial thickness.
A. Model parameters
The reaction-diffusion equations 关Eq. 共11兲兴 have been
solved numerically in the interval of length L⫽128a, where
a is the monomer size contributing to the conformational
entropy f con f 关Eq. 共18兲兴. The grid consisted of 256 points;
the spacing between the grid points is h⫽a/2. The charac-
teristic interaction length l 0 关Eq. 共21兲兴 is another parameter
that determines the internal length scale of the system. For
flexible polymer chains, it is reasonable to assume that the
interaction length l 0 is comparable to the monomer size a.
Hence, for simplicity, we take l 0 ⫽a.
The values of the monomer-monomer and monomer-
polymer Flory-Huggins parameters 关Eq. 共21兲兴 used in the
numerical simulations were ␹ AB ⫽3 and ␹ A P ⫽ ␹ B P ⫽1.25,
respectively. The A and B monomers and the AB copolymer,
which forms in the course of reaction, are mutually incom-
patible at these values of the ␹ parameters.
The solid line in Fig. 5 shows the initial profile of the A
monomers used in the numerical calculations. This curve
corresponds to Eq. 共30兲 with ␾ 0 ⫽0.999 and ␦ 0 ⫽50. For
comparison, the dashed line in Fig. 5 shows the equilibrium
profile of ␾ A at ␹ AB ⫽3. It is worth noting that the equilib-
rium profile is also described by Eq. 共30兲 for certain values
of ␾ 0 and ␦ 0 .
It is convenient to measure the time t in the units of ␶ 0
⫽a 2 /(2D 0 ), which is a period of time necessary for a mono-
mer to diffuse over a distance equal to the monomer size a.
Correspondingly, it takes 1282 ␶ 0 for a monomer to diffuse
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Theoretical model of interfacial polymerization 11449
FIG. 5. The initial conditions used for the numerical calculations. Solid line:
Eq. 共30兲 with ␾ 0 ⫽0.999 and ␦ 0 ⫽50. Dashed line: the equilibrium profile of
␾ A at ␹ AB ⫽3.
over the entire interval L. The dimensionless combination
( ␥ ⫹ ␶ 0 ) provides a measure of how slow 共or fast兲 the forward
polymerization reaction is relative to the diffusive mixing. If
the reaction is fast, ␥ ⫹ ␶ 0 ⬎1, then the polymerization reac-
tion is controlled by diffusion, and the rate equations 关Eqs.
共2兲 and 共27兲兴 should be modified. The value of ␥ ⫹ ␶ 0 ⫽0.2
was used in the numerical calculations in order to ensure that
reaction is in the kinetically controlled regime. Both the re-
versible and irreversible polymerization reactions were con-
sidered. The rate constants of the backward reaction used in
the calculations were ␥ ⫺ ⫽10⫺2 ␥ ⫹ and ␥ ⫺ ⫽0, respectively.
B. Structure of the polymer layer
The theoretical approach developed here allows us to
study the structure of the forming polymer layer in greater
detail than possible with other previous formulations.3–9 In
addition to the polymer volume fraction profile, it provides
information on such characteristics as the spatial distribu-
tions of copolymers of different types and the distribution of
their degrees of polymerization inside the layer.
Let us discuss the structure of a polymer layer obtained
via the numerical simulations at time t⫽5⫻103 ␶ 0 . The solid
line in Fig. 5 shows the initial conditions used. Figures 6 and
7 reveal the structure of the polymer layer formed due to a
reversible interfacial polymerization reaction and Figs. 8 and
9 correspond to the case of an irreversible reaction.
Figure 6共a兲 shows the monomer/polymer composition of
the system with the reversible reactions. The dashed and dot-
ted lines correspond to the profiles of the volume fractions of
the A and B monomers, ␾ A and ␾ B , respectively, and the
solid line shows the distribution of the volume fraction of the
polymer ␾ P ⫽ ␾ AA ⫹ ␾ AB ⫹ ␾ BB . As can be seen in Fig. 6共a兲,
the polymer forms a well-defined layer between the two mo-
nomeric liquids. The layer consists of two thin ‘‘skin’’ areas
at the polymer-monomer interfaces, which are characterized
by a sharp change in the monomer and polymer volume frac-
tions, and the core area, in which the volume fractions vary
smoothly. The monomer content vanishes in the central area
of the layer. Outside the layer (x⬍0.15 and x⬎0.85), the
polymer fraction is seen to be nonzero but small.
Figure 6共b兲 shows the position-dependent overall
number-averaged degree of polymerization, N̄⫽ ␾ P (C AA
⫹C AB ⫹C BB ) ⫺1 , which characterizes the polymer as a
whole. It is seen that the layer confines longer polymer
11450 J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
FIG. 6. The reversible interfacial polymerization: the structure of the react-
ing system at t⫽5⫻103 ␶ 0 . 共a兲 The polymer/monomer composition: ␾ P
共solid line兲, ␾ A 共dashed line兲, and ␾ B 共dotted line兲. 共b兲 The number-
averaged degree of polymerization.
chains than are present in the monomer phases. Inside the
layer, the average degree of polymerization N̄ is also non-
uniform. It is maximal at the center of the layer, and de-
creases gradually towards the skin areas, where it drops
abruptly.
The structure of the polymer layer formed in the course
of the reversible reaction is presented in greater detail in
Figs. 7共a兲 and 7共b兲. Namely, the plots show the spatial dis-
tributions of the volume fractions ␾ i of each type of the
copolymer i⫽AA, AB, BB 关Fig. 7共a兲兴, and the correspon-
dent profiles of the number-averaged degrees of polymeriza-
tion, N̄ i ⫽ ␾ i /C i 关Fig. 7共b兲兴. In these figures, the dashed and
dotted lines describe the AA- and BB-ended chains, respec-
tively, and the solid lines correspond to the AB-ended ones.
Figure 7共a兲 demonstrates that the AB copolymers with
the different types of the end units are distributed nonuni-
formly in the polymer layer. In addition, the profiles of ␾ i
shown in Fig. 7共a兲 are quite different from the profile of the
total polymer volume fraction ␾ P shown in Fig. 6共a兲 共solid
line兲. The central area of the layer is occupied preferentially
by the AB-ended copolymers, while the AA- and BB-ended
chains are concentrated to the right and to the left of the
centerline, i.e., towards the A and B monomeric phases, re-
spectively. Unlike the volume fractions ␾ i the distributions
of the degrees of polymerization N̄ i across the system 关Fig.
7共b兲兴 resemble the general features of the average degree of
polymerization shown in Fig. 6共b兲, although a certain asym-
metry in the profiles of N̄ AA and N̄ BB is noticeable in Fig.
7共b兲.
It is worth noting that both the spatial distributions of the
copolymer volume fractions and their average degrees of po-
lymerization are the result of the concerted action of the
simultaneous processes of the polymerization reaction and
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V. V. Yashin and A. C. Balazs
FIG. 7. The reversible interfacial polymerization: the structure of the poly-
mer layer at t⫽5⫻103 ␶ 0 . 共a兲 Volume fractions of the copolymers: ␾ AA
共dashed line兲, ␾ AB 共solid line兲, and ␾ BB 共dotted line兲. 共b兲 Number-averaged
degrees of polymerization of the copolymers: N̄ AA 共dashed line兲, N̄ AB 共solid
line兲, and N̄ BB 共dotted line兲. 共c兲 The normalized rate of polymerization:
⫺1
R P␥ ⫹ ⫻103 .
the interdiffusion of all of the species present in the system.
Unlike the interdiffusion, the reaction process in the polymer
layer can easily be visualized by plotting the position-
dependent total polymerization rate R P calculated as
R P ⫽ ␥ ⫹ ␾ A 共 ␾ B ⫹C AB ⫹2C BB 兲 ⫹ ␥ ⫹ ␾ B 共 ␾ A ⫹C AB ⫹2C AA 兲
⫺2 ␥ ⫺ 共 C AA ⫹C AB ⫹C BB 兲 . 共31兲
Figure 7共c兲 shows the distribution of the total polymerization
rate in the polymer layer that is formed in the course of the
reversible polymerization reaction. The maximal polymeriza-
tion rate is observed at the center of the layer, i.e., where the
overlap of the monomer concentrations, ␾ A and ␾ B , is maxi-
mal. The polymerization rate decreases gradually towards the
polymer-monomer interfaces. Away from the centerline, the
major contribution to the polymerization rate comes from the
monomer addition to ends of the growing chains. The dis-
tinct behavior of the polymerization rate in the skin areas of
the polymer layer 关Fig. 7共c兲兴 is attributed to reversibility of
the reaction, as is clear from Eq. 共31兲.
Let us now discuss the effect of the reversibility of the
polymerization reaction on the structure of the polymer layer.
J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
FIG. 8. The irreversible interfacial polymerization: the structure of the re-
acting system at t⫽5⫻103 ␶ 0 . The notations are same as in Fig. 6.
The structure of the layer formed in the course of the irre-
versible reaction is presented in Figs. 8 and 9. The notations
used in Figs. 8 and 9 are the same as in Figs. 6 and 7,
respectively.
Comparison of Figs. 6共a兲 and 8共a兲 shows that the revers-
ibility of the reaction does not significantly affect the
polymer/monomer composition profiles of the layer. Never-
theless, the irreversible polymerization reaction results in the
formation of longer polymer chains, as can be seen from
Figs. 6共b兲 and 8共b兲.
Figures 7 and 9, however, reveal that the most dramatic
effect of reversibility is observed in the detailed structure of
the polymer layer. The total amount of the AB-ended copoly-
mers formed in the course of the irreversible reaction is sig-
nificantly lower in comparison with the case of the reversible
reaction 关see Figs. 7共a兲 and 9共a兲兴. Besides, the AB copoly-
mers are located preferably in a rather narrow area around
the center of the layer, as can be seen in Fig. 9共a兲. It is
evident from Figs. 7共b兲 and 9共b兲 that the degrees of polymer-
ization of all the types of the copolymers are greater in the
case of the irreversible reaction. In addition, the shapes of the
distributions of the degree of polymerization across the poly-
mer layer are remarkably different in Figs. 7共b兲 and 9共b兲.
Finally, the reaction zone of the irreversible reaction is lo-
cated well inside the polymer layer 关Fig. 9共c兲兴, and the rate
of polymerization vanishes away from the centerline faster
than observed in Fig. 7共c兲.
It is worth noting that the effects related to the inherent
polydispersity of the system are more important in the case
of irreversible reaction. As shown in Fig. 9共b兲, the spatial
profiles of the degrees of polymerization of the different
types of the copolymers are more nonuniform inside the
polymer layer than in the similar profiles in Fig. 7共b兲. As a
result, the diffusive mobility of the copolymer chains of the
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Theoretical model of interfacial polymerization 11451
FIG. 9. The irreversible interfacial polymerization: the structure of the poly-
mer layer at t⫽5⫻103 ␶ 0 . The notations are same as in Fig. 7.
same type varies more significantly across the polymer layer
in the case of irreversible polymerization reaction.
C. Kinetics of the layer growth
It is seen in Figs. 6共a兲 and 8共a兲 that the volume fractions
of the A and B monomers demonstrate an almost linear de-
crease inside the polymer layer and vanish in a narrow area
around the layer centerline. Furthermore, the polymerization
rate is maximal at the center of the layer according to Figs.
7共c兲 and 9共c兲. These two observations suggest that the
growth of the polymer layer might be controlled by the dif-
fusive transport of the monomers to the zone of the maximal
reaction rate.
Figure 10 confirms that this suggestion is qualitatively
correct. In Fig. 10, the thickness of the polymer layer ⌬
obtained via the numerical simulations is plotted against the
time t in double-logarithmic coordinates. The layer thickness
⌬ was determined as the area where ␾ P ⭓0.5. In Fig. 10, the
thin line corresponds to the power law t 1/2 and is drawn as a
guide to the eye. It is seen that the slope of the thick solid
line, which corresponds to the reversible reaction, is very
close to 0.5 at longer times. Note that the t 1/2 behavior is the
characteristic feature of diffusion controlled growth. How-
ever, the growth of the polymer layer in the course of the
irreversible reaction, which is shown by the thick dashed line
11452 J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
FIG. 10. The kinetics of growth of the polymer layer. Reversible reaction:
thick solid line. Irreversible reaction: thick dashed line. The thin line repre-
sents the purely diffusive power law.
in Fig. 10, is seen to take place slightly slower than pre-
scribed by the purely diffusive t 1/2 power law.
The reason for the difference in the kinetics of the layer
growth in the cases of the reversible and irreversible reaction
observed in Fig. 10 is clarified in Fig. 11. Figure 11 presents
the kinetics of accumulation of the different types of copoly-
mer chains inside the polymer layers, which grow due to the
reversible 关Fig. 11共a兲兴 and the irreversible 关Fig. 11共b兲兴 poly-
merization reactions. The solid thick lines in Figs. 11共a兲 and
11共b兲 correspond to the volume fractions of the AA- and
BB-ended chains taken together and integrated over the layer
thickness. The dashed thick lines correspond to that of the
AB-ended chains. The thin lines in Fig. 11 demonstrate the
power-law growth kinetics with the exponents indicated.
As is evident from Fig. 11共a兲, the formation of all types
of the copolymer chains is controlled by diffusion if the po-
lymerization reaction is reversible. To determine the expo-
nent in the power law t ␣ more precisely, a curve fitting pro-
cedure has been applied at t⬎5⫻103 ␶ 0 . The value of the
FIG. 11. The kinetics of accumulation of the copolymers of different struc-
ture in the polymer layer: 共a兲 reversible reaction, 共b兲 irreversible reaction.
Thick solid lines: ␾ AA ⫹ ␾ BB . Thick dashed lines: ␾ AB . The thin lines rep-
resent the power laws with the exponents indicated.
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V. V. Yashin and A. C. Balazs
FIG. 12. The number-averaged degree of polymerization as a function of the
reaction time for the 共a兲 reversible and 共b兲 irreversible reactions of interfa-
cial polymerization. The type of line corresponds to type of the initial con-
ditions shown in Fig. 5.
power-law exponent ␣ has been found to be 0.52 for the AA-
and BB-ended chains 关thick solid line in Fig. 11共a兲兴, and 0.48
for the AB-ended ones 关dashed thick line in Fig. 11共a兲兴.
However, as can be seen in Fig. 11共b兲, accumulation of the
different types of copolymers follows different scaling laws
if the polymerization reaction is irreversible. Namely, forma-
tion of the AA- and BB-ended chains 关thick solid line in Fig.
11共b兲兴 is controlled by diffusion since the exponent was
found to be 0.51. In contrast, accumulation of the AB-ended
copolymers goes on significantly slower 关dashed thick line in
Fig. 11共b兲兴 with the value of the exponent found to be 0.11.
D. Degree of polymerization and polydispersity
of the reaction product
The product of a polymerization reaction is usually char-
acterized by the values of the number-averaged N̄ n and the
weight-averaged N̄ w degrees of polymerization. The ratio
N̄ w /N̄ n provides a measure of the polydispersity of the reac-
tion product. In order to characterize the polymers obtained
through the interfacial polymerization reaction, we take into
account only those polymer chains that are confined inside
the polymer layer, which is defined as described above. The
values of N̄ n and N̄ w are determined through the average
concentrations C̄ i and the average volume fractions ␾ ¯ of the
i
copolymers of type i⫽AA, AB, BB; the ‘‘bar’’ sign over a
symbol denotes the result of averaging across the layer:
¯ 共 ⌺ C̄ 兲 ⫺1 ,
N̄ n ⫽ ␾ P i i
¯ ⫺1 ⌺ ␾
N̄ w ⫽ ␾ ¯
P i i N̄ wi .
¯ ⫽⌺ ␾¯
In the equations above, ␾ P i i is the total volume frac-
tion of the polymer in the layer and N̄ wi is the weight-
J. Chem. Phys., Vol. 121, No. 22, 8 December 2004
FIG. 13. Polydispersity as a function of the reaction time for the 共a兲 revers-
ible and 共b兲 irreversible reactions of interfacial polymerization. The type of
line corresponds to type of the initial conditions shown in Fig. 5.
averaged degree of polymerization of the copolymer chains
of type i; N̄ wi is determined through Eqs. 共14兲 and 共15兲 using
the obtained values of C̄ i and ␾ ¯ .
i
Figures 12 and 13 present the evolution of the number-
averaged degree of polymerization N̄ n and the polydispersity
N̄ w /N̄ n , respectively, in the course of the reversible 关Figs.
12共a兲 and 13共a兲兴 and irreversible 关Figs. 12共b兲 and 13共b兲兴 in-
terfacial polymerization reactions. In Figs. 12 and 13, the
solid lines denote the results of calculations obtained with
the initial conditions shown in Fig. 5 by the solid line, and
the dashed lines correspond to the equilibrium initial condi-
tions shown in Fig. 5 by the dashed line. As can be seen in
Figs. 12 and 13, the degree of polymerization and the poly-
dispersity are always greater for the polymer sample ob-
tained through the irreversible reaction. It is also evident that
the product of the irreversible polymerization reaction is sus-
ceptible to the initial conditions to a greater extent than the
polymer obtained through the reversible reaction.
It is reasonable to anticipate that in the case of the re-
versible reaction, the polymer MWD converges to the equi-
librium MWD when the formed polymer layer is sufficiently
thick. Opposite to that, the MWD of the polymer obtained in
the course of a irreversible reaction depends significantly on
both the initial conditions and on the reaction time.
V. SUMMARY
We considered a simplified model of interfacial polymer-
ization, in the course of which alternating AB copolymers
form at the interface of immiscible monomeric liquids A and
B. The set of variables chosen for the theoretical description
consists of the volume fractions of monomers A and B, and
the concentrations and the volume fractions of all of the
three kinds of the alternating AB copolymers, i.e., those of
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Theoretical model of interfacial polymerization 11453
the AA-, AB-, and BB-ended chains. This choice of relevant
variables is equivalent to approximating the local MWD of
each type of the copolymer by a distribution similar to the
Flory distribution. The reaction-diffusion equations have
been derived in terms of the chosen variables. Besides
chemical kinetics, the obtained system of equations provides
a description of diffusive intermixing of the following: 共i兲 the
monomer and polymer fractions, 共ii兲 the fractions of different
types of copolymer chains, and 共iii兲 the chains of the same
type with different lengths. As a result, the evolution of the
copolymer MWD due to reaction and diffusion can be deter-
mined, although approximately, together with the monomer/
polymer composition of the system.
The derived equations have been applied to studing in-
terfacial copolymerization in a one-dimensional case, which
corresponds to growth of a copolymer film at a planar inter-
face. The reaction-diffusion equations have been solved nu-
merically for reversible and irreversible copolymerization re-
actions at various initial conditions. Transport of monomers
to the reaction zone has been found to control the growth of
the polymer film in either case. The monomer/polymer com-
position profiles have been found to be similar for the films
forming in the course of the reversible and irreversible reac-
tions. However, these reaction processes result in copolymers
with quite different MWDs and the relative contents of AA-,
AB-, and BB-ended chains. As compared with the reversible
reaction, the structure and MWD of the product of irrevers-
ible copolymerization exhibit a stronger dependence on the
initial conditions, and higher molecular weights can be
achieved.
In future studies, more realistic reaction schemes will be
considered. The approach developed here will be extended to
studying the interfacial polymerization with the effect of hy-
drodynamic interactions, and in the presence of externally
imposed flows.
ACKNOWLEDGMENT
Financial support from the National Science Foundation
and the Dow Chemical Company is gratefully acknowl-
edged.
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