Polymer 210 (2020) 122982

Contents lists available at ScienceDirect

Polymer
journal homepage: http://www.elsevier.com/locate/polymer

Intrinsic kinetics of interfacial polycondensation reactions– the reaction of

mPDA with TMC
Subhalaxmi Behera, Suresh K. Akkihebbal *
Department of Chemical Engineering, Indian Institute of Technology Bombay, Mumbai, 400076, India

A R T I C L E I N F O A B S T R A C T

Keywords: The performance of thin film composite membranes used in reverse osmosis is decided by the thickness and
pH-metry structure of the thin functional layer, which in turn depend on the kinetics of the interfacial polycondensation
Interfacial polycondensation kinetics (IP) reaction which produces this layer. Quantitative determination of these kinetics has been a challenge. In the
Kinetic control
present study, we extend the method of pH-metry developed in our earlier work to the study of IP kinetics, in the
presence of the side reaction of hydrolysis of the organic phase monomer. The method has been used to establish
the kinetics of MPDA –TMC system in the presence and absence of a surfactant, Tween-85. The experimental
method used eliminates all transport resistances, so that intrinsic kinetic control of the observed process is
ensured. The hydrolysis reaction is studied separately by an adaptation of the same method, and those kinetics
are systematically incorporated in the treatment of the data from the IP reaction. The observed kinetics have
been fitted to a lumped kinetic form of the power law type, and show that the reaction is approximately first
order in the acid chloride group concentration, and order 1.6 in the amine group concentration. The surfactant
has been seen to influence the magnitude of the rate constant significantly. The reaction usually stops well short
of 100% conversion of the stoichiometrically limiting monomer, because of the lowering of pH which restricts
the availability of the aqueous phase monomer at the reaction locale.

application in thin film composite membranes, the reaction also finds

1. Introduction
Processes such as distillation and membrane filtration are used to
win potable water from sea/brackish water. Membrane based (reverse
osmosis or RO) processes have several advantages in such applications
over other processes. For example, while distillation process uses 50
times more energy than the theoretical requirement for the production
of potable water from sea water ([1,2]), advances in membrane mate­
rials have continuously reduced the energy cost of membrane-based
desalination processes to the point where near-theoretical limits have
been attained ([3]). Commercial RO membranes are usually of the thin
film composite type, and owe their performance to a thin (100–200 nm)
functional layer, produced usually by an interfacial polycondensation
(IP) reaction carried out on the surface of a support membrane. This
reaction is extremely fast, and the participation of several rate and
equilibrium processes such as solution equilibria, phase separation,
transport factors and reaction kinetics makes its quantitative under­
standing difficult. The reaction uses two immiscible solvents, each of
which contains one of a pair of condensable monomers, with the prod­
uct, an ultra-thin polymer film, forming at the interface. Apart from its
application in such other areas as microencapsulation, and the synthesis
of nano-films and colloids for drug delivery, pharmaceutical separations
etc. For a given chemistry for such a reaction, it has been shown earlier
[4–9] that the physical structure of membrane (and through it, the
functional properties) depends significantly on the kinetics of the reac­
tion and the relative importance of transport and reaction steps. In the
case of membrane forming IP, while the influence of synthesis condi­
tions on membrane structure and performance has been demonstrated
[1,10–20], the link to kinetics is missing because of the challenges in
determining the intrinsic kinetics of the reaction.
In the RO application, while many polymers have been proposed and
some used commercially, aromatic polyamide-based membranes,
formed by the reaction between meta-Phenylene diamine (m-PDA, dis­
solved in water) and trimesoyl chloride (TMC, dissolved in an organic
solvent such as hexane) have come to dominate the market. They show
excellent desalination performance (99.5% salt rejection, a high flux of
42 Lm− 2h− 1) and also exhibit good mechanical strength [21,22]. The
performance of these membranes depends on the thickness [12,23] and
structure of the polyamide thin film [1], which in turn depends on the
kinetic mechanism, so far poorly understood. In this study, we present a

* Corresponding author.
E-mail address: aksuresh@iitb.ac.in (S.K. Akkihebbal).

https://doi.org/10.1016/j.polymer.2020.122982
Received 5 May 2020; Received in revised form 16 August 2020; Accepted 23 August 2020
Available online 29 August 2020
0032-3861/© 2020 Elsevier Ltd. All rights reserved.
S. Behera and S.K. Akkihebbal
Nomenclature
CAO initial m-PDA concentration in water
CAT Total amine concentration in water
CBO initial TMC concentration in hexane
C–NH2 functional group concentration of amine
C–COCl functional group concentration of acid chloride
h hydrogen ion concentration
K1 Equilibrium constant of di protonated m-PDA
K2 Equilibrium constant of mono protonated m-PDA
K3 Equilibrium constant of HCl
KW ionic product of water
k rate constant
method and results on the determination of the kinetics of the interfacial
polycondensation reaction between mPDA and TMC.
From the earliest studies on the reaction by Morgan and co-workers
at DuPont, the accumulated evidence indicates that the reaction takes
place on the organic side of the interface. Enkelmann and Wegner [24]
were the first to propose a kinetic model for IP, considering the film
formation to be dictated by concurrent diffusion and reaction. Other
works have followed [25–29] with varied conceptualisation of the
interfacial reaction and film formation mechanism. Berezkin and
Khokhlov [30], and more recently, Dhumal and Suresh [7] have pre­
sented reviews. In general, three different modelling approaches are
seen. One approach [25,31] considers the overall process as composed
of diffusion (of the aqueous phase monomer through the already formed
film) in series with an interfacial reaction at the phase boundary, with
the product of the reaction adding to the thickness of the film. Freger
et al. [27], on the other hand, have described a multi-stage mechanism
involving incipient film formation, a slowdown step, and diffusion
limited growth [26–28]. The ‘film’, in their approach, forms at the limit
as polymerization as crosslinking reactions lead to progressive viscosi­
fication and ultimately, gelification [23,29]. Nadler and Srebnik [32]
studied the kinetics of initial film formation through a simulation
incorporating these principles, neglecting the hydrolysis of acid chloride
monomer. In the third approach [4,5,33], reaction and diffusion (and
also other mass transport processes) are both considered with the so­
lution thermodynamics for the oligomers being invoked to explain film
formation. The properties of the film depend on whether the system is
under diffusional, kinetic or mixed control. It is thus important to know
the intrinsic kinetics of the reaction to distinguish between competing
models and to come to useful conclusions on the influence of preparation
conditions on film thickness and structure.
The challenges in experimental kinetic studies of IP reaction are due
to the speed of the reaction, the thinness of the polymer film and the
zone of reaction, intervention of transport factors to disguise the
intrinsic kinetics, and the occurrence of a side reaction, of hydrolysis of
the organic monomer with production of an acid by-product (depending
on the chemistry employed) [16,17,24,34]. Attempts to measure inter­
facial polymerization kinetics have included monitoring membrane
mass or thickness, or monomer concentrations, with time [24,25,
34–41]. Such measurements have generally been unable to predict
detailed kinetics of fast forming films and in producing quantitative
descriptions of kinetics. Attempts have also been made to relate changes
in membrane properties with time to the progress of reaction, using
techniques such as pendent drop tensiometry, light reflectometry [36],
and diffuse reflectance spectroscopy [12], again mainly capturing
qualitative features. These techniques have been recently reviewed in
Behera and Suresh [9,42,43]. More recently, in a technique that shows
promise, Nowbahar et al., 2018 [44] have used multiple-beam inter­
ferometry in a micro-fluidic device to track the spatial and temporal
evolution of amine monomer concentration near the interface and
2
Polymer 210 (2020) 122982
Kp partition co-efficient of unprotonated amine into oil phase
m-PDA meta phenylene diamine
A un-protonated m-PDA
A+ mono-protonated m-PDA
A++ di-protonated m-PDA
rA moles of amine functional group (-NH2) consumed per unit
area per second
S total surface area available
TFCM Thin film composite membrane
TMC tri-mesoyl chloride
SSQ Sum of squares error
α Order with respect to amine monomer
β Order with respect to acid chloride monomer
determine its flux from the aqueous phase.
In a recent study [9], we have developed a pH-metry based method
for the study of intrinsic kinetics of IP by systematically eliminating (or
rendering unimportant) all transport resistances. The technique was
used to determine the kinetics of mPDA-TMC reaction, under conditions
so chosen that the side reaction of hydrolysis of the organic monomer
may be neglected. In a subsequent study [42,43] we used an extension of
the method to determine the kinetics of hydrolysis of TMC in an inter­
facial setting. In the present work, we combine the two methods to arrive
at a general method of studying the kinetics of interfacial poly­
condensations in the presence of hydrolysis as a possible side-reaction.
The method has been used to determine and quantify the kinetics of
the reaction between mPDA and TMC.
2. Experimental
2.1. Materials
De-ionized water, purged with Nitrogen at a pressure of 0.3 Bar to
expel any dissolved carbon dioxide, was used to prepare the aqueous
phase. The aqueous phase monomer m-PDA, of 99% purity (monomer
A), was obtained from Merck, Switzerland. The organic solvent, n-
Hexane (99% pure) was obtained from Merck, Germany. The organic
phase monomer TMC (Tri-mesoyl chloride), 98% pure (monomer B),
was obtained from Sigma-Aldrich. Tween-85 (Fluka, Switzerland) was
used to stabilize the o/w emulsion in which the reaction was carried out
in those experiments in which the surfactant effect was meant to be
studied.
2.2. Experimental method
The experimental procedure is basically the same as detailed in our
earlier papers [9,42,43].The basic principle underlying the method is to
exploit the pH changes (in the aqueous phase), caused by the reaction, to
monitor the progress of reaction. The reaction is carried out in a
two-phase reaction mixture (an oil-in-water emulsion) at a stirring speed
of 5000 RPM, so that (i) external mass transfer resistances are elimi­
nated, and (ii) the polymer film produced is stripped off the surface of
the organic drop as soon as it forms. Transport resistances are thus
eliminated and the reaction proceeds under kinetic control. The drop in
pH is due to the consumption of amine and generation of hydrochloric
acid; the latter being in part due to the polyamidation reaction between
amine and acid chloride, and in part to the side reaction of interfacial
hydrolysis of the acid chloride monomer. As the reaction takes place on
the organic side of the interface, only un-protonated amine can partition
into organic phase from aqueous phase and react with the acid chloride
monomer to form the cross-linked polyamide. Mechanistically, the
following steps may be identified:
S. Behera and S.K. Akkihebbal Polymer 210 (2020) 122982

❖ Protonation of the diamine in the aqueous phase to an extent

− COCl + H2 O→ − COOH + HCl (2)
determined by the prevailing pH.
❖ Partitioning of the un-protonated diamine into the organic phase. A charge balance in the aqueous phase containing amine and hy­
❖ The (main) reaction of the un-protonated amine with the acid chlo­ drochloric acid (generated from the IP reaction as well as hydrolysis of
ride monomer, the acid chloride monomer) gives, at any stage in the reaction,
❖ The parallel side reaction of hydrolysis of the acid chloride
monomer, [H+ ] + [A+ ] + 2[A++ ] = [OH− ] + b + [Cl− ]IP (3)
❖ Transfer of the HCl produced in the main and side reactions to the
where the chloride ions coming from the two reactions are distin­
aqueous phase, and consequent adjustment of pH
guished, b standing for the contribution from hydrolysis, and [Cl− ]IP , for
the contribution from IP.
We assume the first, second and last steps to be instantaneous, and
Let X = Conversion of mPDA =
hence, that the measured rate of pH variation in the aqueous phase is
(moles of mPDA converted /moles of mPDA taken). Because of the low
directly related to the rate of the reaction steps.
solubility of mPDA in the organic phase, it is reasonable to assume that
Each experiment was repeated at least twice, and with sufficient
virtually all the monomer that has transferred over to the organic phase
care, good reproducibility could be achieved. Information on repro­
has reacted. Conversion X can therefore be calculated from the moles of
ducibility checks is presented in the Supplementary information.
mPDA that have disappeared from the aqueous phase. Further, again
The principal variables in the kinetic study are the concentrations of
because of the small solubility of mPDA in the organic phase, TMC is in
the two monomers and the phase volume ratio, the two together
large excess in the reaction zone (compared to mPDA) for most of the
determining the monomer mole ratio R. A surfactant is often used in the
reaction, irrespective of the value of R. Hence, chances are that both the
conduct of IP, particularly in applications such as microencapsulation.
amino groups of a converted mPDA molecule would have reacted; X
Experiments to study the effect of surfactant concentration on poly­
would therefore also represent the conversion of amino groups to a very
condensation kinetics were conducted with a phase volume ratio (V:Org
good approximation:
VAq) of 4.583:259 mL, and with monomer concentrations as CAO = 2.2E-
03 mol/dm3 and CBO = 0.113 mol/dm3, giving a monomer mole ratio R moles of ( − NH2 ) converted/2
X= = X−
= 0.91. Four different surfactant concentrations, 0, 0.5, 2 and 4 vol%, moles of ( − NH2 ) taken/2
NH2

were used in these experiments, thus covering concentrations both

from which, we have,
below and above the critical micelle concentration (CMC) of Tween-85,

Moles(− NH2 )converted in IP = 2CAO VAq (X) = 2CAO VAq (X) = moles(HCl)IP formed

1.395 vol%. Tables 1 and 2 show the experimental plan for the detailed
kinetic studies. The experiments described in Table 1 were carried out at where CA0 is the total mPDA concentration taken in the aqueous phase at
the same phase volume ratio as mentioned above, and the effect of the start of the reaction. Therefore, we have
monomer concentrations is studied in the presence (4 vol%) and absence
Concentration of HCl in aq. phase due to IP = [Cl− ]IP = 2CAO X
(0%) of surfactant. The experiments in Table 2 were essentially carried
out to provide a check on the kinetics; in these experiments, some of the
concentrations used in the experiments of Table 1were repeated, but at 3.2. Dissociation equilibrium
three different volume ratios. The experiments were planned in such a
manner as to cover a wide range of R values (0.23 < R < 3.71) on either In the aqueous phase, the following processes are at equilibrium:
side of stoichiometric equivalence (R = 1.5).
A++ A+

NH2+ − ̂
R − NH2+ ⇔ NH2 − ̂
R − NH2+ + H +
3. Theory
NH2+ − R − NH2 ⇔ NH2 − R − NH2 + H +
3.1. Kinetic interpretation for the interfacial polycondensation reaction
between mPDA and TMC Hence, letting ‘h’ stand for the hydrogen-ion concentration,
A+ h Ah
The reactions involved may be represented as follows. The main K1 = , K2 = +
A++ A
reaction is.

where A denotes mPDA and B, TMC. In addition, the hydrolysis of the We have, for the total concentration of amine monomer in the
acid chloride at the interface must be considered: aqueous phase at any stage in the reaction:

3
S. Behera and S.K. Akkihebbal Polymer 210 (2020) 122982

Table 1
dVOrg Cb K dVAq b
Experimental plan for kinetics study, effect of monomer concentration. One set − = SkH Cb = (6)
of these experiments were carried out with 4% surfactant, and another, without dt K+h dt
surfactant. Volume of aqueous phase = 259 mL; volume of organic phase =
where Cb = Acid chloride group concentration in organic phase, and S =
4.583 mL.
interfacial area available.
CBO (mol/dm3) R CBO/CAO
Eq. (6) can be rewritten as follows
5.20E-04 1.13E-01 3.84 217.31 ( ) ( )
5.20E-04 5.70E-02 1.94 109.62 db S K
= k H Cb (7)
5.20E-04 3.80E-02 1.3 73.08 dt VAq K+h
5.20E-04 2.80E-02 0.95 53.84
1.10E-03 1.13E-01 1.79 102.73 The concentration of acid chloride Cb is in turn related to b and X,
1.10E-03 5.70E-02 0.9 51.82 since.
1.10E-03 3.80E-02 0.59 34.55 Moles of -COCl in organic phase = Initial moles of -COCl − (moles of
1.10E-03 2.80E-02 0.45 25.46
2.20E-03 1.13E-01 0.94 51.36
-COCl)consumed in IP − (moles of -COCl) consumed in Hydrolysis
2.20E-03 5.70E-02 0.46 25.91
VOrg Cb = 3CBO VOrg − 2CA0 XVAq − bVAq (8)
2.20E-03 3.80E-02 0.3 17.27
2.20E-03 2.80E-02 0.23 12.73
VAq
Cb = 3CBO − (2CA0 X + b) (9)
VOrg
CAT = A + A+ + A++
Using this in Eq. (7) and substituting for X from (5), we get
from which, using the equilibrium relations, the concentrations of

⎛ ⎛ ( )⎞⎞
2
( ) ( ) h− KW
− b + CDA0 Kh2 + K2h1 K2 ( )
db S ⎜ VAq 2VAq ⎜ h ⎟⎟ K
= kH ⎜
⎝3CBO − b − CA0 ⎜
⎝ ( ) ⎟⎟
⎠⎠ (10)
dt VAq VOrg VOrg 2 K+h
2 + D1 Kh2 + K2h1 K2

different forms of the amine monomer may be written: where.

CA0 (1 − X) + CA0 (1 − X)h ++ CA0 (1 − X)h2

A= ; A = ; A = CAO=Initial mPDA concentration in aqueous phase
D K2 D K1 K2 D
CAT = mPDA concentration at time ‘t’ in aqueous phase
where CBO=Initial acid chloride monomer concentration in organic phase
Cb = Acid chloride group concentration in organic phase
h h2 VAq = Volume of aqueous phase
D=1 + +
K2 K1 K2 VOrg = Volume of organic phase
S = Total interfacial area available
Using these in the charge balance eq. (3),
h = Hydrogen ion concentration in the aqueous phase
CA0 (1 − X)h 2CA0 (1 − X)h2 KW
h+ + = + 2CA0 X + b (4)
K2 D K1 K2 D h With the above development, the kinetics of IP can be determined
from measured pH-time data as follows:
which may be rearranged to:
( ) ❖ Determination of time vs b profile from measured pH-time data
(experimental) of IP kinetics using eq. (10). Eq (10) was solved in the
2
h − KhW − b + CDA0 Kh2 + K2h1 K2
X= ( ) (5) present work using the function ODE15 in MATLAB
❖ Determination of X-t data using the pH- time data and the results of
2
2CA0 + CDA0 Kh2 + K2h1 K2
the above calculation.
Eq. (5) gives the amine conversion in terms of the hydrogen ion
concentration and the extent of hydrolysis. The hydrolysis reaction at Once the conversion-time behavior is thus extracted, an appropriate
the aqueous-organic phase interface has been studied in our earlier work kinetic expression may be fitted.
[43], in which the rate of hydrolysis, i.e., the moles of -COCl hydrolysed
per sec, was modelled as:

Table 2
Experimental plan for kinetics study (to check the robustness of kinetic measurements). These experiments were carried out without any added surfactant.
CAO (mol/dm3) CBO (mol/dm3) nAO (mol) nBO (mol) V Org(mL) V Aq (mL) R CBO/CAO

1.10E-03 1.13E-01 2.80E-04 5.20E-04 4.58E+00 2.59E+02 1.86E+00 1.03E+02

1.10E-03 3.80E-02 2.80E-04 5.20E-04 1.38E+01 2.59E+02 1.86E+00 3.46E+01
1.10E-03 2.10E-02 2.80E-04 5.20E-04 2.50E+01 2.59E+02 1.86E+00 1.91E+01
5.20E-04 2.10E-02 1.40E-04 5.20E-04 2.50E+01 2.59E+02 3.89E+00 4.04E+01
1.10E-03 2.10E-02 2.90E-04 5.20E-04 2.50E+01 2.59E+02 1.84E+00 1.91E+01
2.20E-03 2.10E-02 5.70E-04 5.20E-04 2.50E+01 2.59E+02 9.20E-01 9.55E+00

4
S. Behera and S.K. Akkihebbal
Fig. 1. Effect of acid chloride hydrolysis on kinetics, time versus functional group conversion:(a, c) without surfactant; (b, d) 4% surfactant., where R (Only Re­
action); R + H (Both reaction and Hydrolysis).
4. Results and discussion
4.1. The need to account for hydrolysis in interpreting pH data
In our earlier work [42], the competitive side reaction of hydrolysis
of the organic monomer was shown to follow 1st order kinetics with
respect to the acid chloride monomer concentration (see eq. (7)). In
Fig. 1, we compare the conversion-time behavior from pH measure­
ments for a typical experiment, as calculated with (curve R) and without
(curve R + H) consideration of the hydrolysis reaction. The comparison
has been made for the same concentration of TMC (0.113 mol/dm3), but
two different concentration of mPDA (0.0022 mol/dm3, panels (a), (b) &
0.00052 mol/dm3, panels (c), (d)). For each case, the effect of two
different concentrations of surfactant are presented. Fig. 1 shows that,
the cumulative effect of hydrolysis is felt at larger times and is the more
serious, the lesser the surfactant concentration and the lesser the amine
monomer concentration, for a given TMC concentration. This shows that
the methodology developed in Ref. [9], which neglects the hydrolysis
reaction completely, is only justifiable under certain circumstances. In
general, the hydrolysis reaction has to be accounted for in order to
Fig. 2. Effect of surfactant concentration on polyamidation kinetics, CAO = 0.0022 mol/dm3, CBO = 0.113 mol/dm3, R = 0.91, VOrg = 4.583 mL, VAq = 259 mL.
5
Polymer 210 (2020) 122982
correctly interpret the pH curves for kinetics of IP. In what follows, all
pH-time data have been interpreted accounting for hydrolysis.
4.2. Effect of surfactant and monomer concentrations on reaction kinetics
Since the reactions being considered occur at or near the interface,
the presence of surfactant could have a significant influence on the ki­
netics, through (for example) barrier and/or micellar transport effects;
this has been shown in our earlier work [42] for hydrolysis. The sur­
factant used here is Tween-85, whose critical micellar concentration is
1.395% (by volume). In order to study the influence of surfactant con­
centration, we have carried out experiments over a range of surfactant
concentrations spanning the region from below to above CMC keeping
other conditions constant, as described earlier. pH-time data and the
calculated conversion-time profiles are shown in Fig. 2.
Fig. 2 shows that the maximum conversion achieved is around
20–40% in all cases (this is also seen in the case of the results shown in
Fig. 1), and that the reaction is essentially complete within 150 s. While
part of the reason for the reaction terminating is because of hydrolysis
(which consumes a part of the acid chloride that could otherwise be
S. Behera and S.K. Akkihebbal Polymer 210 (2020) 122982

Fig. 3. Effect of acid chloride concentration on kinetics with no surfactant, at CAO = 0.0011 mol/dm3 (a) pH-time data, (b) Calculated conversion-time profile.

Fig. 4. Effect of acid chloride concentration on kinetics with 4% surfactant content at CAO = 0.0011 mol/dm3. (a) pH-time data, (b) Calculated conversion-time
profile. The insets show the data and calculations for the first 20 s of reaction.

available for polyamidation), the more important reason is the lowering the reaction kinetics. In our earlier paper [9], we have discussed the
of pH, which makes the amine monomer unavailable for reaction by methodology to determine the interfacial area and its correlation with
decreasing the fraction of the amine that is un-protonated. As in the case stirring speed of reaction, surfactant concentration, acid chloride
of hydrolysis, the rate of polyamidation is higher for higher surfactant monomer concentration for the system and experimental set up used in
concentrations, the difference in initial rates being especially noticeable this work. In the present study, we have used those experimentally
for surfactant concentrations above CMC. A higher interfacial area is one determined interfacial areas.
obvious reason for this; some micellar transport of the aqueous phase
monomer to the reaction site also cannot be ruled out. 5. A kinetic model
Figs. 3 and 4 show the effect of monomer concentrations on kinetics,
from experiments listed in Table 2. While Fig. 3 is for the case of no Since the reaction occurs on the organic side of the interface, we have
surfactant, Fig. 4 is for the case in which 4% surfactant was used. For the used a surface-area based rate law for the consumption of amine.
experiments shown in Fig. 3, the initial concentration of the amine Rate of consumption of mPDA per unit area per unit time = r = moles
monomer was kept the same (0.0011 mol/dm3; see supplementary in­ m-PDA reacted per unit area per unit time
formation for similar data for other amine concentrations), but the
− 1 dVAq CAT α
initial concentration of TMC was varied. Fig. 4 shows similar data, but = r = k(C− NH2 )Org (Cb )β
S dt (11)
for experiments carried out at 4 vol% surfactant. The insets in this figure
CAT = CAO (1 − X)
show short time behavior of the kinetics, in the first 20 s. It is seen that
higher concentrations of the organic monomer result in faster rates of IP If Kp represents the partitioning of the unprotonated amine between
in general. As mentioned earlier, the reaction is much faster for the same the aqueous and organic phases, i.e.,
monomer concentrations in the presence of surfactant. In some of the ( )
experiments in Fig. 4, especially those with a high initial rate, a hump is Concentration of mPDA in organic phase
Kp =
seen in the data. As shown in our earlier work [9], this is not a kinetic Concentration of un − protonated mPDA in aqueous phase Equilibrium
feature but an artefact introduced because of the high rate of reaction
when a large interface area is available. (C− NH2 )Org =2KP (Concentration of unprotonated mPDA left, at conversion X)
In the next section, we discuss the fitting of a kinetic expression to
explain these features quantitatively.
2KP CAO (1 − X)
(C− NH2 )Org = (12)
D
4.3. Interfacial area
The expression for Cb has already been discussed in Eq. (9). Eq. (11)
As the reaction between m-PDA and TMC monomers is an interfacial thus becomes
polycondensation polymerization, interfacial area has an influence on

6
S. Behera and S.K. Akkihebbal Polymer 210 (2020) 122982

( )( ( ))α ( )β
dX S 1− X VAq Table 3
=k 2Kp CAO 3CBO − (2CAO X + b) (13) Optimized value of kinetic parameters in the experiments for the effect of sur­
dt VAq CAO D VOrg
factant concentration on kinetics at CAO = 0.0022 mol/dm3, CBO = 0.113 mol/
The above differential Eq. (13) may be integrated and fitted to the dm.3.
data in a least squares sense to get optimized value of the orders of re­ [Surfactant] (vol S (m2) k (mol/m2 s(mol/dm3) α β SSQ
action “α” and “β”, and the rate constant, “k”. The known parameter %) α+β
)
values used for the optimization programme are as follows: 0 10.40 128.63 1.82 1.07 0.006
Notation Description 0.5 11.40 139.37 1.70 1.00 0.015
2 16.32 170.00 1.60 1.00 0.025
K1 Equilibrium dissociation constant of di-protonated m-PDA in water, =
4 16.72 202.37 1.63 0.96 0.007
10− 2.65 [45]
K2 Equilibrium dissociation constant of mono-protonated m-PDA in water,
= 10− 4.88 [45]
KW Ionic product of water 5.1. Results from parameter fitting
Kp Partition co-efficient of mPDA into organic phase = 0.0077 [9]
S Total surface area available for the IP reaction = 10.355 m2 when As observed from the experimental result on the effect of surfactant
reaction occurring with no surfactant content, and 16 m2 with 4% concentration on IP kinetics, it is clear that there is a quantitative dif­
surfactant content [9]
ference in the kinetics between surfactant concentrations above and
below CMC (Fig. 2). This could at least partly be due to the effect of the
Parameter estimation strategy surfactant on interfacial area. To get more insight into whether the
The model has three parameters k, α and β, which have to be surfactant really has an effect on kinetics, effect of acid chloride
determined from experimental data. This was done using least squares monomer concentration on kinetics both in absence and presence of
regression as follows: eq. (13) was integrated for chosen value of k, α and surfactant (Figs. 3 and 4) has been examined.
β using the MATLAB function ‘ode45’ to obtain a simulated conversion-
time profile, which was then compared with the experimental profile 5.1.1. Effect of surfactant concentration on kinetics
and a sum of squares of error calculated as Fig. 5 shows the fit of the model to the data from experiments carried
out to examine the effect of surfactant concentration on kinetics. The
n ( )2
∑ XExpti − XSimi optimized values of α, β, and k are given in Table 3. The model is seen to
SSQ =
i=1
XSimi capture the qualitative features of the kinetics very well for all surfactant
concentrations. The value of the fitted rate constant increases with in­
The parameters k, α and β were then regressed through a minimi­ crease in surfactant concentration in the range (2*102 to 1.2*102 (mol/
zation of SSQ using the non-linear fitting subroutine ‘lsqnonlin’ in m2 s (mol/dm3)α+β), α is in the range of (1.6 to1.8) and β is nearly 1
MATLAB. Here XExpti is the functional group amine conversion at ith irrespective of surfactant concentration.
experimental point, and XSimi the corresponding functional group amine The value of these kinetic parameters may be compared with the
conversion as estimated by the model, for the same experimental point. values in our earlier paper [9] They are quite similar and follow the
It was observed that the overall quality of fit could be improved same trend as discussed in the Supplementary information, see Section
considerably by omitting very short time data in certain cases. These 2.4.
were usually the experiments without surfactant, in which the amine
conversion is slow to start, but takes off after a few seconds. This practice 5.1.2. Fit of the model to the experimental data without added surfactant
was accordingly followed. Fig. 6 shows a sample of kinetic fitting of experimental data with eq.

Fig. 5. Fit of experimental data with the kinetic model for effect of surfactant concentration on kinetics with CBO = 0.113 mol/dm3, CAO = 0.0022 mol/dm3, (R =
0.91), VOrg = 4.583 mL, VAq = 259 mL.

7
S. Behera and S.K. Akkihebbal Polymer 210 (2020) 122982

Fig. 6. Theoretical validation of experimental data theory on effect of acid chloride concentration on kinetics with 0% surfactant content, CAO = 0.0011 mol/dm3,
(0.46 < R < 1.88), time versus functional group amine conversion.

Table 4
Optimized value of reaction kinetics parameters with no added surfactant, at
CAO = 0.0011 mol/dm.3.
CAO CBO R S k (mol/m2 s α β SSQ
(mol/ (mol/ (m2) (mol/dm3)
dm3) dm3) α+β
)

0.0011 0.113 1.88 10.4 100.01 1.63 1.05 0.013

0.0011 0.057 0.95 10.4 100.13 1.63 1.06 0.009
0.0011 0.037 0.63 10.4 94.81 1.6 1.03 0.008
0.0011 0.028 0.4 10.4 86.48 1.63 1.02 0.011

Fig. 8. Effect of amine concentration on kinetics with no surfactant content in

the TMC emulsion, amine concentration versus ‘α’

Fig. 7. Effect of amine concentration on rate of reaction with 0% surfactant
content, acid chloride concentration versus rate constant.
(13), for experiments carried out with different initial monomer con­
centrations, in the absence of any surfactant. For the runs shown, the
mPDA concentration was kept constant at 0.0011 mol/dm3 and the TMC
concentrations were varied. Comparisons for other mPDA concentra­
tions are available in the Supplementary information (section 2.2,
Figs. S4 & S5). The overall fit quality is again seen to be very good in all
cases. The optimized value of α, β, and k are shown in Table 4. It is seen
that the values of α and β are nearly the same in all cases, and similar to
values in Table 3. While the values of k show some scatter, Fig. 7 shows
the k values plotted against CB0 for all concentrations of CA0, and it is
seen that values lie in a narrow band with no systematic trends.
While a sample of the fitting is demonstrated in the figures discussed
here, more details are available in the Supplementary information
(Figs. S6 & S7) and a comprehensive summary follows. While the fit in
these cases is generally satisfactory, in some cases the large time data
were not so well fitted (see for example Fig. S4 in Supplementary In­
formation). One reason for this is the nature of the calibration curve
between pH and conversion – the curve at low pH is quite flat as
mentioned in Fig. 6 of [9], and therefore pH is not a sensitive measure of
conversion at high conversions.
Considering the parameter estimates for all cases, it was found that
the order of reaction with respect to TMC was fairly close to 1 in all
cases. The order with respect to mPDA, while it also varied only within a
narrow range (1.5–1.8), did show a tendency to increase slightly with
mPDA concentration, see Fig. 8. The mPDA concentration at the site of
reaction is subject to ionic equilibria in the aqueous phase and the
partitioning equilibria between the phases, and small errors in the

8
S. Behera and S.K. Akkihebbal Polymer 210 (2020) 122982

Fig. 9. Theoretical validation of experimental data with theory for effect of acid chloride concentration on kinetics with 4% surfactant content, CAO = 0.0011 mol/
dm3, (0.46 < R < 1.88) Time versus functional group amine conversion.

Fig. 10. Effect amine and acid chloride concentration on rate of reaction with
4% surfactant content, acid chloride concentration versus rate constant. Fig. 11. Effect of acid chloride concentration on the rate constant with 0% &
4% surfactant.

Table 5 5.1.3. Fit of the model to the experimental data with 4 vol% surfactant
Optimized value of reaction kinetics parameters with 4% surfactant content at Fig. 9 represents fit of eq. (13) to experimental data with different
CAO = 0.0011 mol/dm.3.
acid chloride concentration and constant amine concentration (i.e. CAO
CAO CBO R S k (mol/m2 s α В SSQ = 0.0011 mol/dm3) with 4% Surfactant content in the dispersed phase
(mol/ (mol/ (m2) (mol/dm3)
as discussed in section-4.2 (fits for other amine concentrations are pre­
dm3) dm3) α+β
)
sented in Supplementary information). The optimized kinetic parameter
0.0011 0.113 1.88 16.5 160.00 1.5 1.02 0.010 values are given in Table 5. The overall fit quality is good for all con­
0.0011 0.057 0.95 16.5 170.00 1.52 1.07 0.016
centration of acid chloride as shown in Fig. 9 (. Fig. 10 shows the vari­
0.0011 0.037 0.63 16.5 170.62 1.61 0.86 0.017
0.0011 0.028 0.46 16.5 180 1.6 0.94 0.009 ation in the value of the rate constant with the acid chloride
concentration, and similar conclusions obtain as in the case of the
parameter values for the no-surfactant case.
equilibrium constants for these processes can contribute to some un­ Here the reaction kinetics has been studied at the same mole ratios as
certainty in the value of this reaction order. The rate constant was found used in the experiments without surfactant. The difference in kinetics,
to be about 102 (±20)mol/m2s(mol/dm3)α+β as shown in Table-(3, 4 and between the experiments with and without surfactant is that the reaction
S1, S2 in supplementary information). rate is faster in the former case. The reaction completes within 50 s
(Fig. 4) in the experiments with 4-vol% surfactant content while it takes

9
S. Behera and S.K. Akkihebbal Polymer 210 (2020) 122982

Fig. 12. Effect of acid chloride concentration on kinetics (R = Constant, CAO = 0.0011 mol/dm3), Time versus functional group conversion.

Table 6
Optimized value of reaction kinetics parameters with 0% surfactant content at CAO = 0.0011 mol/dm3, effect of acid chloride conc. on kinetics.
CAO (mol/dm3) CBO (mol/dm3) VOrg (mL) R S (m2) α β k (mol/m2s (mol/dm3) α+β) SSQ

0.0011 0.113 4.583 1.88 10.4 1.65 1.08 110.23 0.019

0.0011 0.038 13.75 1.88 31.07 1.7 0.87 80 0.016
0.0011 0.021 25 1.88 56.5 1.64 1.02 114.56 0.017

Fig. 13. Effect of amine concentration on kinetics (R = Varied, CBO = 0.021 mol/dm3), Time versus functional group amine conversion.

10
S. Behera and S.K. Akkihebbal
Table 7
Optimized value of reaction kinetics parameters with 0% surfactant content at CBO = 0.021 mol/dm3, effect of amine concentration on kinetic.
CAO (mol/dm3) CBO (mol/dm3) VOrg (mL) R S (m2)
0.00052 0.021 25 3.98
0.0011 0.021 25 1.88
0.0022 0.021 25 0.96
200–400 s in the absence of surfactant as seen in Fig. 3. The fitted rate
constant with 4% surfactant content is in the range of (200 ± 20 (mol/
m2 s (mol/dm3)) while for the same reaction condition with no surfac­
tant content as mentioned in Fig. 11, it of order of 100 ± 20 (mol/m2 s
(mol/dm3)).
5.3. A check on the robustness of the kinetic model and parameter
estimates
In order to demonstrate the robustness of our kinetic interpretations
an additional two sets of experiments were carried out. The first set was
with a constant amine concentration and different acid chloride con­
centrations, achieved by changing the volume of dispersed phase but
keeping the moles of acid chloride monomer in the dispersed phase, the
same. This results in constant monomer mole ratio (R) of two monomers,
but different concentration ratios as shown in Table 2. The results of
fitting the data from these experiments are shown in Fig. 12. The
parameter estimates are given in Table 6. The parameter values returned
are in the same range as in the earlier experiments with a constant
volume ratio.
The second set of experiment as shown in Fig. 13 is with the same
acid chloride monomer concentration (0.021 mol/dm3), but different
amine monomer concentration. In this case, the variation is achieved at
the same volume of continuous phase by varying the number of moles of
mPDA. This results in a variation in mole ratio (R) of two monomers as
shown in Table 2. Comparing these R values with those in Table 1, we
find similar R values, but at different concentration ratios in the two
cases.
The parameter values returned from the fitting procedure for these
experiments are shown in Table 7, and are once again seen to be in the
same range as in the earlier cases, thus lending confidence to the kinetic
description used.
See Table 6
The results presented in Figs. 12 and 13 as well as Tables 6 and 7
show that the proposed kinetic expression captures the effect of con­
centrations of the monomers on the kinetics in a consistent manner,
across experiments carried out at constant phase volume ratio, constant
R, and in experiments with the same mole ratios but different concen­
tration ratios.
6. Conclusion
In this paper, we have developed a method for the kinetic study of IP
reactions in which the pH variation in the aqueous phase can be used as
an indicator of the extent of reaction. The hydrolysis of the organic
phase monomer, a common side reaction in IP systems, can potentially
queer the interpretation of kinetics since that reaction also causes a
change in pH. This has been taken care of by studying the kinetics of
hydrolysis independently by an adaptation of the same experimental
technique, and accounting for those kinetics in the interpretation of IP
kinetics in a systematic manner. The method has been demonstrated for
the mPDA-TMC system, whose kinetics have been established in this
study. It is seen that the effect of hydrolysis becomes prominent at large
times of reaction, at low surfactant concentrations, and for low con­
centrations of the aqueous phase monomer for a given concentration of
the organic phase monomer. For the system studied, the lowering of pH
due to the release of the byproduct HCl leads to a cessation of reaction at
amine conversions of 40% or less. The presence of a surfactant has been
Polymer 210 (2020) 122982
α β k (mol/m2s (mol/dm3) α+β) SSQ
56.5 1.62 0.99 102.48 0.026
56.5 1.64 1.02 114.56 0.017
56.5 1.67 1.12 83.75 0.015
shown to speed up the reaction, as has also been demonstrated for the
side reaction of hydrolysis in our earlier work [42,43]. A kinetic
expression of the power law type has been fitted to the experimental
data and has been shown to provide a satisfactory fit, with consistent
parameter values, over the entire range of conditions investigated. The
order of reaction is about 1.6 with respect to amine concentration
(m-PDA) and one with respect to acid chloride concentration (TMC). The
rate constant of the reaction is about (102 ±20) [mol/m2s
(mol/dm3)α+β] in the absence of surfactant, and increases with
increasing surfactant concentration, with values going up to (2*102±20)
[mol/m2s (mol/dm3)α+β] at 4% surfactant concentration.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.polymer.2020.122982.
References
[1] R.J. Petersen, Composite reverse osmosis and nanofiltration membranes, J. Membr.
Sci. 83 (1993) 81–150.
[2] D.S. Sholl, R.P. Lively, COMMENT, Nature 532 (2016) 6–9.
[3] M. Elimelech, W.A. Phillip, The future of seawater desalination: energy,
technology, and the environment, Science 333 (2011) 712–717, https://doi.org/
10.1126/science.1200488.
[4] S.K. Yadav, K.C. Khilar, A.K. Suresh, Microencapsulation in polyurea Shell :
kinetics and film structure, AIChE J. 42 (1996) 2617–2626.
[5] S. Dhumal, S. Wagh, A.K. Suresh, Interfacial polycondensation—modeling of
kinetics and film properties, J. Membr. Sci. 325 (2008) 758–771, https://doi.org/
10.1016/j.memsci.2008.09.002.
[6] S.K. Yadav, K.C. Khilar, A.K. Suresh, Release rates from semi-crystalline polymer
microcapsules formed by interfacial polycondensation, J. Membr. Sci. 125 (1997)
213–218.
[7] S.S. Dhumal, A.K. Suresh, A comprehensive model for kinetics and development of
film structure in interfacial polycondensation, Polymer 50 (2009) 5851–5864,
https://doi.org/10.1016/j.polymer.2009.09.072.
[8] S.S. Dhumal, A.K. Suresh, Understanding interfacial polycondensation:
experiments on polyurea system and comparison with theory, Polymer 51 (2010)
1176–1190, https://doi.org/10.1016/j.polymer.2010.01.004.
[9] S. Behera, A.K. Suresh, Kinetics of interfacial polycondensation reactions-
Development of a new method and its validation, Polymer 127 (2017) 28–44,
https://doi.org/10.1016/j.polymer.2017.08.026.
[10] M. Ding, A. Szymczyk, F. Goujon, A. Soldera, A. Ghoufi, Structure and dynamics of
water confined in a polyamide reverse-osmosis membrane: a molecular-simulation
study, J. Membr. Sci. 458 (2014) 236–244, https://doi.org/10.1016/j.
memsci.2014.01.054.
[11] Cadotte John E., United States Patent [19], 1977.
[12] T.D. Matthews, H. Yan, D.G. Cahill, O. Coronell, B.J. Mariñas, Growth dynamics of
interfacially polymerized polyamide layers by diffuse reflectance spectroscopy and
Rutherford backscattering spectrometry, J. Membr. Sci. 429 (2013) 71–80.
[13] T. Zhe, C. Shengfu, P. Xinsheng, L. Zhang, G. Congjie, Polyamide membranes with
nanoscale Turing structures for water purification, Science 360 (2018) 518–521,
doi:US2013/0154292A1.
[14] H. Mariën, I.F.J. Vankelecom, Optimization of the ionic liquid-based interfacial
polymerization system for the preparation of high-performance, low-fouling RO
membranes, J. Membr. Sci. 556 (2018) 342–351, https://doi.org/10.1016/j.
memsci.2018.03.071.
[15] H. Mariën, L. Bellings, S. Hermans, I.F.J. Vankelecom, Sustainable process for the
preparation of high- performance thin-film composite membranes using ionic
liquids as the reaction medium, CHEMSUSCHEM 9 (2016) 1–12, https://doi.org/
10.1002/cssc.201600123.
11
S. Behera and S.K. Akkihebbal
[16] H. Mariën, I.F.J. Vankelecom, Transformation of cross-linked polyimide UF
membranes into highly permeable SRNF membranes via solvent annealing,
J. Membr. Sci. 541 (2017) 205–213, https://doi.org/10.1016/j.
memsci.2017.06.080.
[17] V.T. Do, C.Y. Tang, M. Reinhard, J.O. Leckie, Degradation of polyamide
nanofiltration and reverse osmosis membranes by hypochlorite, Environ. Sci.
Technol. 46 (2012) 852–859, https://doi.org/10.1021/es203090y.
[18] X. Song, S. Qi, C.Y. Tang, C. Gao, Ultra-thin, multi-layered polyamide membranes:
synthesis and characterization, J. Membr. Sci. 540 (2017) 10–18, https://doi.org/
10.1016/j.memsci.2017.06.016.
[19] C.Y. Tang, Y.-N. Kwon, J.O. Leckie, Probing the nano- and micro-scales of reverse
osmosis membranes-A comprehensive characterization of physiochemical
properties of uncoated and coated membranes by XPS, TEM, ATR-FTIR, and
streaming potential measurements, J. Membr. Sci. 287 (2007) 146–156, https://
doi.org/10.1016/j.memsci.2006.10.038.
[20] C.Y. Tang, Y.-N. Kwon, J.O. Leckie, Effect of membrane chemistry and coating
layer on physiochemical properties of thin film composite polyamide RO and NF
membranes I . FTIR and XPS characterization of polyamide and coating layer
chemistry, Desalination 242 (2009) 149–167, https://doi.org/10.1016/j.
desal.2008.04.003.
[21] A.K. Ghosh, B.-H. Jeong, X. Huang, E.M.V. Hoek, Impacts of reaction and curing
conditions on polyamide composite reverse osmosis membrane properties,
J. Membr. Sci. 311 (2008) 34–45, https://doi.org/10.1016/j.memsci.2007.11.038.
[22] A.F. Ismail, M. Padaki, N. Hilal, T. Matsuura, W.J. Lau, Thin film composite
membrane — recent development and future potential, Desalination 356 (2015)
140–148, https://doi.org/10.1016/j.desal.2014.10.042.
[23] Y. Zhang, N.E. Benes, R.G.H. Lammertink, Visualization and characterization of
interfacial polymerization layer formation, Lab Chip 15 (2015) 575–580, https://
doi.org/10.1039/c4lc01046a.
[24] V. Enkelmann, G. Wegner, Mechanism of interfacial polycondensation and the
direct synthesis of polyamide membranes, Makromol. Chem. 177 (1976)
3177–3189, https://doi.org/10.1002/macp.1976.021771106.
[25] S.K. Yadav, A.K. Suresh, K.C. Khilar, Microencapsulation in polyurea shell by
interfacial polycondensation, AIChE J. 36 (1990) 431–438, https://doi.org/
10.1002/aic.690360312.
[26] R. Oizerovich-Honig, V. Raim, S. Srebnik, Simulation of thin film membranes
formed by interfacial polymerization, Langmuir 26 (2010) 299–306, https://doi.
org/10.1021/la9024684.
[27] V. Freger, S. Srebnik, Mathematical model of charge and density distributions in
interfacial polymerization of thin films, J. Appl. Polym. Sci. 88 (2003) 1162–1169,
https://doi.org/10.1002/app.11716.
[28] V. Freger, Kinetics of film formation by interfacial polycondensation, Langmuir 21
(2005) 1884–1894, https://doi.org/10.1021/la048085v.
12
Polymer 210 (2020) 122982
[29] D.G. Cahill, V. Freger, S.-Y. Kwak, Microscopy and microanalysis of and
nanofiltration, MRS Bull. 33 (2008) 27–32.
[30] A.V. Berezkin, R. Khokhlov Alexei, Mathematical modeling of interfacial
polycondensation, J. Polym. Sci. B Polym. Phys. 44 (2006) 2698–2724.
[31] M. Sirdesai, K.C. Khilar, A model for microencapsulation in polyurea shell by
means of interfacial polycondensation, Can. J. Chem. Eng. 66 (1988).
[32] R. Nadler, S. Srebnik, Molecular simulation of polyamide synthesis by interfacial
polymerization, J. Membr. Sci. 315 (2008) 100–105.
[33] S.K. Karode, S.S. Kulkarni, A.K. Suresh, R.A. Mashelkar, New insights into kinetics
and thermodynamics of interfacial polymerization, Chem. Eng. Sci. 53 (1998)
2649–2663.
[34] P.J. Bradbury, J.H. Crawford, Kinetics of an interfacial polycondensation reaction
Part 1 .-Hydrolysis of terephthaloyl chloride, Trans. Faraday Soc. V (1967)
185–191, https://doi.org/10.1039/tf9686401337.
[35] J. Ji, M. Mehta, Mathematical model for the formation of thin-film composite
hollow fiber and tubular membranes by interfacial polymerization, J. Membr. Sci.
192 (2001) 41–54.
[36] G.-Y. Chai, W.B. Krantz, Formation and characterization of polyamide membranes
via interfacial polymerization, J. Membr. Sci. 93 (1994) 175–192.
[37] L.J.J.M. Janssen, K. te Nijenhuis, Encapsulation by interfacial polycondensation. I.
The capsule production and a model for wall growth, J. Membr. Sci. 65 (1992)
59–68.
[38] C. Wang, D. Wang, W. Chiu, L. Chen, Study on the kinetics of interfacial
polycondensation for polyarylate, Angew. Makromol. Chem. 248 (1997) 123–137.
[39] Y. Lee, H. Tsai, N. Tsing, V. Polyarylates, The influence of phase transfer agents on
the interfacial polycondensation, J. Polym. Sci. Polym. Chem. 26 (1988)
2039–2046.
[40] K. Bouchemal, F. Couenne, S. Briancon, H. Fessi, M. Tayakout, Polyamides
Nanocapsules : modeling and wall thickness estimation, AIChE J. 52 (2006)
2161–2170, https://doi.org/10.1002/aic.
[41] J. Zhang, J.H. Atherton, P.R. Unwin, Investigation of the kinetics and mechanism
of acid chloride hydrolysis in an oil/water system using microelectrochemical
measurements at expanding droplets (MEMED), Langmuir 20 (2004) 1864–1870,
https://doi.org/10.1021/la0355951.
[42] S. Behera, A.K. Suresh, Kinetics of interfacial hydrolysis of an aromatic acid
chloride, Chem. Eng. Res. Des. 146 (2019) 154–161, https://doi.org/10.1016/j.
cherd.2019.03.030.
[43] S. Behera, A.K. Suresh, Data on of interfacial hydrolysis kinetics of an aromatic acid
chloride, Data in Brief 26 (2019), https://doi.org/10.1016/j.dib.2019.104337.
[44] A. Nowbahar, V. Mansard, J.M. Mecca, M. Paul, T. Arrowood, T.M. Squires,
Measuring interfacial polymerization kinetics using microfluidic interferometry,
J. Am. Chem. Soc. 140 (2018) 3173–3176, https://doi.org/10.1021/jacs.7b12121.
[45] John A. Dean, Handbook of Chemistry, fifth ed., 2005, https://doi.org/10.1080/
10426919008953291.