European Polymer Journal 132 (2020) 109719

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Temperature effect on aqueous NH4CN polymerization: Relationship T

between kinetic behaviour and structural properties
⁎
Itziar Masa, José L. de la Fuenteb, Marta Ruiz-Bermejoa,
a
Centro de Astrobiología (INTA-CSIC), Dpto. Evolución Molecular, Ctra. Torrejón-Ajalvir, km 4, Torrejón de Ardoz, 28850 Madrid, Spain
b
Instituto Nacional de Técnica Aeroespacial “Esteban Terradas” (INTA), Ctra. Torrejón-Ajalvir, km 4, Torrejón de Ardoz, 28850 Madrid, Spain

A R T I C LE I N FO A B S T R A C T

Keywords: Herein, a kinetic analysis for aqueous NH4CN polymerizations is presented, which is consistent with an auto-
HCN polymers catalytic model when polymerizations are performed at relatively high temperatures, 80–90 °C. Further ex-
Precipitation polymerization periments at lower polymerization temperatures, approximately 50 °C, have demonstrated that this relevant
Kamal model prebiotic reaction follows nth-order kinetics rather than an autocatalytic mechanism. In addition, the sol frac-
Autocatalysis
tions of these precipitation polymerizations have been evaluated by UV–Vis measurements, which also show a
Kinetic
Spectroscopy
mechanistic shift with the reaction temperature. This change in the kinetic behaviour led to the proposal of a
simple empirical methodology to describe both chemical- and diffusion-controlled regions. Despite the simplicity
of the approach based on the Hill equation, fundamental kinetic parameters, such as the activation energy, can
be determined in the diffusion-free zone. These results motivated a systematic structural characterization study
of the respective insoluble polymers by means of elemental analysis, FT-IR and NMR spectroscopies and XRD. All
these kinetic and structural analyses confirmed that the temperature has a significant effect on the poly-
merization kinetic of the system, on the macrostructural features and properties of the HCN-based polymers, and
presumably also on the polymerization pathways. These data increase our knowledge about the chemistry of this
particular family of HCN polymers, which is currently of interest both in the field of materials science and in
prebiotic chemistry and astrobiology.

1. Introduction
Currently, the development of new and advanced functional mate-
rials must be considered from an environmental perspective. This
starting point implies the challenge of finding sustainable and green
synthetic methods. The use of solvents such as water and low reaction
temperatures are fundamental conditions to obtain efficient, friendly
and low-cost industrial processes. In this sense, the production of HCN-
derived polymers might be a good example, because this heterogeneous
family of substances can be obtained under a wide range of experi-
mental conditions, e.g., using water as a solvent in spontaneous poly-
merization reactions, or by bulk polymerizations at not relatively high
temperatures [1]. These complex macromolecular systems show inter-
esting properties [2], leading to their consideration as promising mul-
tifunctional materials with potential applications as coating materials,
semiconductors, photocatalysts or capacitors (see, e.g., [2–8]). How-
ever, their structural characteristics and, by extension, their final
properties and hence their potential applications depend directly on the
experimental synthetic conditions used for their production, such as
initial pH, the salinity of the aqueous environment, temperature, pre-
sence of oxygen, or the reaction time [see e.g. 2, 9–12]. Therefore, a
comprehensive knowledge of the kinetic history of HCN polymer for-
mation and their respective structural features are prerequisites to
properly tune the properties of the desired reaction products. Thus, in
the present case, the effect of the temperature is systematically studied
for aqueous NH4CN polymerization considering several approaches and
models to explain the kinetics of this precipitating reaction as well as its
influence on the structural nature of the insoluble polymers synthe-
sized.
In a previous study, a Kamal autocatalysis kinetic model was pro-
posed to describe the formation of insoluble NH4CN polymers and gel
fractions during the polymerization of NH4CN in aqueous medium at
relatively high temperatures, 75–90 °C [12]. Under those conditions,
the maximum reaction rate occurred at low conversions, and an auto-
catalytic kinetic model for these precipitation polymerizations must be
considered. According to the behaviour of an autocatalytic poly-
merization, the equation dα/dt = k αm (1-α)n, where m and n are re-
action orders and k is the reaction rate constant, could be used.

⁎
Corresponding author.
E-mail address: ruizbm@cab.inta-csic.es (M. Ruiz-Bermejo).

https://doi.org/10.1016/j.eurpolymj.2020.109719
Received 27 February 2020; Received in revised form 20 April 2020; Accepted 21 April 2020
Available online 01 May 2020
0014-3057/ © 2020 Elsevier Ltd. All rights reserved.
I. Mas, et al.
However, due to the very complex pathway proposed for the cyanide
polymerization [2], where several events occur simultaneously, kinetic
models with multiple rates can provide more accurate results. There-
fore, the well-known Kamal-Sourour kinetic model was chosen. This
model involves two rate constants, k1 and k2 (with two different acti-
vation energies and pre-exponential factors), and has the following
form, dα/dt = (k1 + k2 αm)·(1-α)n, where n and m are the reaction
orders. In this case, the influence of the reaction products on the re-
action rate is given by the term k2αm. The application of this phenom-
enological kinetic model instead of mechanistic models was based on
two relevant aspects: on the one hand, the simplicity of the phenom-
enological models, and on the other hand, as was indicated above, the
extraordinary complexity of the aqueous heterogeneous NH4CN poly-
merization, which is convoluted with hydrolysis, oxidation and other
thermally initiated chemical reactions [2]. However, certain limitations
were found when this phenomenological approach was employed. Low
correlation coefficients were obtained, especially at lower polymeriza-
tion temperatures, and unrealistic reaction orders were determined. In
addition, an analysis of the activation energy (Ea) was only performed
from three temperatures in a narrow range, and then, a reliable de-
termination of the Arrhenius parameters was not achieved. These re-
sults indicated a change in the model with the polymerization tem-
perature and/or with the conversion range under study. Thus, herein,
new experimental data sets have been presented for medium tem-
peratures, 50–70 °C, and replicated for 80 and 90° C in order to solve
some of these considerations.
Moreover, aqueous NH4CN polymerizations at lower temperatures,
below 38 °C, were previously monitored by UV–Vis spectroscopy in an
attempt to model the kinetics of NH4CN polymer formation through the
spectroscopic characteristics of the sol fractions [10]. In that case, the
Hill equation, y = Vmax [xn/(kn + xn)], where n is the Hill coefficient
(unitless) that reflects the steepness (sigmoidicity) of the curve, was
used taking in consideration the evolution of the absorbance relation-
ships at A230/A300 during the polymerization process for the sol frac-
tions. The band at ~300 nm decreases in a time-dependent manner up
its disappearance, which indicates the transformation of cyanide and/or
the tetramer diaminomaleonitrile (DAMN, likely the main intermediate
in the HCN or cyanide polymerization, as will be explained later) in
other products. In parallel, the narrow peak at ~230 nm increases with
time, thus indicating the reaction polymerization progress. The Hill
equation is widely used for the description of biochemical, geochemical
and chemical processes (for more detail about the Hill function, see the
references cited in [10]). This simple model was very useful to provide
a general view of the influence of the air, ammonium cation and salty
environment in the kinetic process of NH4CN polymerization at 20 and
38 °C. Here, this experimental modelling for the sol fractions is ex-
tended to a range of temperatures from 50 to 90 °C for NH4CN polymers
as a complementary study of the gravimetric measurements and kinetic
analysis from the gel fractions indicated above.
On the other hand, the black insoluble solids obtained in the water
polymerization of NH4CN from 50 to 90 °C were characterized using
several techniques, such as elemental analysis, FT-IR spectroscopy,
solid-state 13C NMR spectroscopy, and XRD. In addition, the stability of
these solids against acid hydrolysis was studied. All this structural in-
formation may contribute to explaining the complex pathways of pro-
duction of HCN polymers and to relating the changes in the kinetic and
mechanistic approaches described herein with the main plausible in-
termediate molecules implicated in the formation of this relevant
polymeric system. The production of HCN polymers in water environ-
ments is known to be a robust process. The results presented here and
those recently reported in the literature corroborate this fact as well as
the direct dependence of the properties of the final polymerization
products on the experimental conditions of the reaction. These con-
clusions deepen and extend our vision about the nature and chemistry
of these fascinating polymeric systems, known as HCN polymers, which
have recently been of high interest in materials science but are also
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European Polymer Journal 132 (2020) 109719
considered primary substances in prebiotic chemistry and astrobiology.
2. Experimental section
2.1. Aqueous NH4CN polymerizations
NH4CN polymers were synthesized from equimolar water solutions
of NaCN and NH4Cl (1 M) under atmospheric pressure. The poly-
merization reactions were performed in 20 mL glass vials fitted with
Teflon/silicone septa and placed into heated metal blocks with tem-
peratures of 50, 60 and 70 °C as well as 80 and 90 °C, as comparative
experiments at higher temperatures, finding a good correlation between
the previous data [12] and those reported herein (Fig. S1). When the
desired time was achieved, the reaction mixture was immediately
cooled, and the final suspensions were filtered. The reaction products
consisted of both soluble and insoluble materials. Insoluble black solids
and brown solutions (gel and sol fractions, respectively) were collected,
and both were freeze-dried until a constant weight was reached, re-
sulting in black powdered solids (insoluble polymers) and brown solids
(soluble oligomers/polymers). Polymer insoluble conversions, α, were
determined by a gravimetric method and were calculated as the initial
weight of the cyanide added to the system [α = (final weight of in-
soluble NH4CN polymer/initial weight of CN−) × 100].
The insoluble black polymers were characterized by elemental
analysis, FT-IR spectroscopy, 13C NMR spectroscopy, and X-ray dif-
fraction. Additionally, the acid-hydrolysed products of these gel frac-
tions were characterized by elemental analysis, FT-IR spectroscopy and
UV–Vis spectroscopy.
On the other hand, the lyophilized sol fractions were analysed in a
similar way to previously described for the crude reactions of the
NH4CN polymerizations below 38 °C by UV–Vis spectroscopy [10]. In
the present case, 4 mg of the dried sol samples were dissolved in 1 mL of
water. The suspensions were centrifuged at 13000 rpm for 10 min, and
the UV–Vis spectra of the supernatants were recorded.
2.2. Elemental analysis
The NH4CN polymers were examined for the determination of the
mass fractions of carbon, hydrogen and nitrogen using a Perkin Elmer
elemental analyser, model CNHS-2400. The percentages of oxygen in
the samples were obtained by calculating the differences.
2.3. FT-IR spectroscopy
Diffuse reflectance spectra were acquired in the 4000–400 cm−1
spectral region using an FT-IR spectrometer (Nicolet, model NEXUS
670) configured with a drift reflectance accessory (Harrick, model
Praying Mantis DRP) mounted inside the instrument compartment. The
spectra were obtained in CsI pellets, and the spectral resolution was
2 cm−1.
13
2.4. C CP MAS-NMR
13
C CP MAS-NMR spectra were obtained using a Bruker Advance
400 spectrometer and a standard cross-polarization pulse sequence.
Samples were spun at 10 kHz, and the spectrometer frequency was set
to 100.62 MHz. A contact time of 1 ms and a period between successive
accumulations of 5 s were used. The number of scans was 5000, and the
chemical shift values were referenced to tetramethylsilane (TMS).
2.5. Powder X-ray diffraction
Powder X-ray diffraction was performed using a Bruker D8 Eco
Advance with Cu Kα radiation (λ = 1.542 Å) and a Lynxeye XE-T linear
detector. The X-ray generator was set to an acceleration voltage of
40 kV and a filament emission of 25 mA. Samples were scanned
I. Mas, et al. European Polymer Journal 132 (2020) 109719

between 5° (2θ) and 60° (2θ) using a step size of 0.05° and a count time
of 1 s, using the Bragg–Brentano geometry.

2.6. UV–Vis spectroscopy

The UV–Vis spectra were recorded in a Nanodrop 1000 spectro-

photometer (Thermo Scientific, Madison, Wisconsin, EE. UU) in the
range of 220 to 730 nm at room temperature. To obtain reliable spec-
troscopic data, it was necessary to pre-process the raw spectra before
the kinetic analysis. Thus, the spectra were normalized and then
smoothed by applying the Savitzky-Golay algorithm.

2.7. Hydrolysis conditions

Twenty milligrams of selected black insoluble polymers at limit

conversions were hydrolysed in flame-sealed glass vials using 0.5 mL of
6 M HCl at 110 °C for 24 h. The crude reactions were centrifuged and
washed with water (13000 rpm/10 min and 0.5 mL of water × 3). The
pellets and the supernatants were collected and freeze-dried until a
constant weight was achieved.

3. Results and discussion

3.1. Polymerization kinetics

3.1.1. Analysis of the production of insoluble NH4CN polymers by

gravimetry
The isothermal polymerization kinetics of NH4CN were system-
atically investigated at five different temperatures between 50 and
90 °C at a 10 °C interval. Fig. 1a) shows the plot of the experimentally
determined conversion (α) versus polymerization time (t) for all tem-
peratures. As can be seen, the percentage conversion increased rapidly
with the reaction time at the initial stage, followed by the next stage,
where the rate of increase decreased asymptotically thereafter until the
end of the polymerization process. This general characteristic beha-
viour of NH4CN polymerization in water can be described by the Hill
equation [12], as it has been determined (lines curves). This proposal is
based on a previous work [10], where the sol fractions during this
polymerization process were analysed by means of spectroscopic mea-
surements as indicated in the Introduction. It is important to note that
excellent correlation coefficient values (R2), higher than 0.98, were
found, which are collected in Table S1, together with the parameter of
the Hill equation. Although, in principle, some of these parameters have
no physical meaning, it is significant that the n exponent decreases as
the polymerization temperature does, except for the temperature of
50 °C.
The Hill function gives a correct fit to all experimental set data, and
the profile of these curves indicates that diffusion effects occur when
the reaction progresses, as can be observed in Fig. 1a). From these
curves, it is possible to build an empirical model [13], which requires
much less overall investment in modelling when little is known about
the physical and chemical phenomena underlying the process, as occurs
in this case. Therefore, at the initial regime or stage, where the reaction
kinetics are likely chemically controlled, the instantaneous poly-
merization rate (Rp) can be determined through the slope of the straight
lines drawn (dashed lines). The obtained values were used later for the
activation energy (Ea) analysis. The other distinctive parameter of the
second kinetic stage is the limit conversion (α∞), which was determined
from the last region, where the curves are asymptotic to the time-axis
(dashed lines), and these values are compiled in Table S1. Here, a de-
crease in the reaction species’ mobility occurs, and the polymerization
reaction becomes diffusion-controlled because of an increase in the
molecular weight and/or the crosslinking of the polymer chains. The
α∞ values vary between 35 and 44% conversion, reaching the highest
plateau conversion at lower reaction temperatures. The crossing point
of both lines can give an estimation of the time of conversion (αonset)
Fig. 1. a) Degree of conversion α and b) the conversion rate dα/dt vs reaction
time of aqueous NH4CN polymerization at different isothermal temperatures.
Note: The insets have the same axis legends as that of the full figure.
where the reaction changes from a chemically controlled to diffusion-
controlled process. In Fig. 1a), a solid black line showing the division of
chemically controlled and diffusion-controlled regions is drawn. The
αonset values for all the polymerizations under study are also presented
in Table S1, taking a constant value of approximately 25% for the
higher temperatures and after increasing as the polymerization tem-
perature decreases.
An advantage of this approach is its simplicity in presentation,
though there may be some inconsistency in the transition region be-
tween both stages. In contrast, the current empirical model can be very
useful in the early stage of polymerization, as observed in the plot inset.
Thus, the fitting curves of α-t conform to an apparent “self-accelera-
tion”, S shape, for the lower temperatures, especially at 50 °C. However,
this profile for the autocatalysis process is not as evident for 80 and
90 °C. This preliminary idea must be confirmed through phenomen-
ological kinetic models; consequently, new attempts to fit the data were
made in order to clarify the uncertainties mentioned regarding the
applicability of the Kamal model.
Before this analysis, it is important to note that in general, the ki-
netic models of thermosetting polymers fall into two main types: (1)
nth-order models and (2) autocatalytic models. This classification is
based on the fact that there are two categories of crosslinking reactions
differentiated by whether the maximum rate of reactions takes place at
zero conversion or at a finite conversion value. The nth-order model is

3
I. Mas, et al.
often simply expressed by the reaction rate equation, dα/dt = k(1-α)n,
where n is the reaction order, dα/dt is the reaction rate, and k is the
apparent rate constant. This equation assumes that n is a constant in-
dependent of temperature and conversion a predicts a linear relation-
ship between ln(dα/dt) and ln(1-α). In most works so far, these as-
sumptions were accepted, though there are often large discrepancies
from reality. However, the nth-order model cannot describe the pro-
gress of those systems in which autocatalysis is present, for those cases
the well-known Kamal model can be used.
From the experimental data of conversion as a function of poly-
merization time, it is possible to obtain the reaction rate, dα/dt, by
differentiating the data sets for the α-t curves, as shown in Fig. 1b). In
the inset plot of this figure, it is possible to see in detail the profiles of
the new curves for the first stage of the polymerizations. An unclear
tendency is found for the derivatized experimental data at poly-
merization temperatures of 90 and 80 °C; however, the conversion rate
data at lower temperatures present less dispersion, as can be observed
in the new plot inset. In addition, these temperatures of 70, 60 and
50 °C have not been previously studied, and therefore, an exhaustive
analysis must be completed. Regardless of the difficulties in following
the polymerization at the fast-early stage using gravimetric measure-
ments, the results for 70 °C indicate that the conversion rate increased
rapidly at the start of the reaction to a maximum and then decreased
exponentially to a minimum value. This behaviour, typical of an au-
tocatalytic process, is not as obvious for the data set at 60 °C, and even
for 50 °C, where the maximum conversion rate appears to occur at t = 0
or α = 0, in which case the nth-order model could be considered.
Attempts were made to curve fit the dα/dt data – α plots, as shown
in Fig. 2, using the Kamal expression for the obtained values from the
polymerization temperatures of 70 and 60 °C. The kinetics parameters
k1, k2, m and n from this curve fitting are given in Table S2. These
kinetic parameters were calculated by using multi-variable nonlinear
regression, and the square of the coefficient of correlation was also
collected in this table. It can be seen from this figure (solid lines) and
Table S2 that a good correlation was only found for 70 °C. Although the
error of fitting was acceptable considering experimental uncertainties
and the fact that a reduced number of kinetic data sets are fitted to the
phenomenological kinetic model, these kinetic parameters were in
concordance with those reported for our group at higher temperatures,
90 and 80 °C (see Table 1 in reference [12]). Thus, the k2 values are
much higher than k1, and at the same time, m ≈ 1.5 and n take a high,
unrealistic value. In contrast, the statistical parameter R2 was not good
for the polymerization temperature of 60 °C when a Kamal model was
Fig. 2. Rate of change of conversion dα/dt vs conversion degree α for aqueous
NH4CN polymerization at different isothermal temperatures. Symbol experi-
mental values of the conversion rate. Lines: calculated values.
4
European Polymer Journal 132 (2020) 109719
used. In this case, k1 ≤ 0.001 and k2 and m are very low; therefore, the
autocatalytic effect is very weak and can be considered negligible. The
polymerization reaction resembles an nth-order process, but the appli-
cation of this kinetic model does not improve the correlation coefficient
when a nonlinear multiple regression method is used. Nevertheless, a
significantly better regression coefficient is obtained when a lineariza-
tion of the nth-order equation is applied. This fact can be observed
through the plot inset in Fig. 2, where ln(dα/dt) versus ln(1-α) is pre-
sented for these temperatures. The polymerization kinetics at 50 °C
could not be fitted properly to the Kamal model, but the nth-order
equation can correctly predict the experimental data, as illustrated in
this figure (dashed lines). However, it is observed that the opposite
behaviour occurs at this lowest temperature. In this case, the relation-
ship between ln(dα/dt) and ln(1-α) presents a low linearity, though a
better correlation coefficient, R2 > 0.96, is found when the other
method of fitting is used.
All these results for both kinetic models are summarized in Table S2
for the three temperatures under study. In any case, the results indicate
that the reaction order “n” may not be constant throughout the range of
temperatures. In addition, these results reflect a possible change in the
mechanism. At higher temperatures, the polymerization can follow the
autocatalytic kinetic model rather than an nth-order kinetic model.
3.1.2. Activation energy analysis
Consistent estimation of the Arrhenius parameters requires one to
conduct experiments at three or more temperatures. In addition, typi-
cally, the temperature range should not be less than 20–40 °C. However,
certain limitations found in a preliminary work led us to calculate this
relevant kinetic parameter with only three temperatures and in a
narrow temperature range from 75 to 90 °C [12]. Although the new
experiments presented in this work covered a rather wide temperature
range, the polymerization reaction under study seems to be dominated
by a dissimilar mechanism at different stages of the process and, at the
same time, involves an autocatalytic mechanism operating at higher
temperatures that shifts to an nth-order reaction as the polymerization
temperature is reduced.
This fact makes it complicated to address the Ea determination, and
therefore, this determination has been done from the values of reaction
rate obtained from the first polymerization stage, which is chemically
controlled. The usual Arrhenius dependence constructed from the Rp
values in Table S1 followed a straight line over the range of 50 to 90 °C,
as shown in Fig. 3. The slope of this plot yielded Ea values of 67 kJ/mol.
This result is quite consistent with the values reported in a previous
work, where the apparent iso-conversional activation energy was de-
scribed [12]. In the bibliography, there are very few reports about the
cyanide polymerization rate, and to our knowledge, this is the first time
Fig. 3. Arrhenius plot of the polymerization rate in the first stage vs the tem-
perature reciprocal.
I. Mas, et al.
Fig. 4. Degree of conversion vs reaction time of the aqueous polymerization of
NH4CN at different isothermal temperatures. Symbol experimental values.
Lines: calculated values according to different kinetic models. The inset has the
same axis legends as that of the full figure.
that an average value for the activation energy has been calculated for
this particular case of HCN polymers. In a pioneering work, Ferris and
co-workers indicate that the rate of aqueous cyanide oligomerization to
DAMN is not influenced by the presence of nucleophiles and that is only
dependent on the initial pH [14]. However, it was recently shown that
ammonium ions influence the cyanide polymerization rate [10], and
Schwartz and Goverde showed that cyanohydrins significantly accel-
erate the rate of HCN oligomerization to DAMN [15]. Therefore, new
studies are necessary to complete a global vision of cyanide poly-
merization, taking into account the activation energy values to obtain a
comprehensive understanding of the real catalysts in this complex
Fig. 5. Evolution of UV–Vis spectra at different reaction times for aqueous NH4CN polymerization at different isothermal temperatures. The UV–Vis spectra of the
NH4CN polymers synthesized at 80 °C were also recorded but for clarity are not shown in the figure.
5
European Polymer Journal 132 (2020) 109719
reaction.
3.1.3. Theoretical predictions from kinetic experimental parameters
At this point, it is interesting to compare the experimental data with
the simulated predictions calculated from the kinetic parameters gen-
erated from both models. Fig. 4 shows the comparison of experimental
data versus either Kamal or nth-order model calculated values. As
shown in this figure, the deviations are evident, and neither model fits
the conversion data for the two stages of polymerization. For example,
for the highest temperature of 70 °C, an acceptable correlation is found
between the experimental values and the calculated data through both
models, but only at the early stage, where the reaction kinetics are
likely chemically controlled, but later, the theoretical maximum con-
version is higher than that obtained experimentally. This similar ten-
dency is also observed for the reaction at 60 °C, whose experimental
data were also fit to Kamal and nth-order models, as clearly observed in
the plot inset. However, the change in the kinetic model to the nth-
order model does not provide a real improvement to represent the
process kinetics at a lower temperature of 50 °C.
On the other hand, from the determination of Arrhenius parameters
examined in the previous section, it is possible to estimate the con-
version rate at another temperature outside the temperature range
considered. Therefore, as indicated in Fig. 3, a value of Rp = 2.6·10−3
h−1 was calculated for a polymerization temperature of 38 °C. This
predictable value could be confirmed when compared with further
experimental data obtained in previous works from our laboratory
[10,11,16]. Although this set of data at 38 °C is scarce, it is sufficient to
indicate the known kinetic trend; then, the empirical model based on
the Hill function was again applied, as shown in Fig. 4. From this fitting,
the following kinetic parameters were obtained: a maximum conversion
of 44% and a reaction rate into the chemically controlled stage of
2.1·10-3 h−1, as indicated in this plot. Both values are expected from the
kinetic analysis done so far.
I. Mas, et al.
Fig. 6. Polymerization profiles based on the absorbance ratio for the poly-
merization reactions carried out from 50 °C to 90 °C. The lines represent the fit
to the Hill function. The inset has the same axis legends as that of the full figure.
3.1.4. Approach to the kinetics by UV–Vis spectroscopy
In the previous sections and according to a gravimetric method, the
reaction process under study seems to be dominated by different me-
chanisms at distinct temperatures, with an autocatalytic reaction
shifting to an nth-order kinetic process as the polymerization tem-
perature decreases. This dependence should also be reflected in the
kinetics of the formation of the soluble oligomers/polymers, i.e., in the
characteristics of the sol fractions obtained in the same way as the gel
fractions, taking into account that it has been proposed that the soluble
NH4CN oligomers/polymers are the intermediate products of the cya-
nide polymerization reactions and that the precipitation of the black
polymers is only a change in the cross-linking grade of the system [10].
Fig. 7. C/N, C/H, C/O and N/O molar ratios for NH4CN polymers synthesized at different temperatures as a function of the conversion. For clarity, the results for
80 °C are not shown in the figure.
6
European Polymer Journal 132 (2020) 109719
In general, an evolution in the UV–Vis spectra of the sol fractions
with the polymerization temperature is observed, with those obtained
at 90 °C more complex than those obtained at 50 °C (Fig. 5). Therefore,
the Hill correlation was newly applied to the relationship A230/A300 for
NH4CN polymerization at 50 and 60 °C, and a relatively good fit be-
tween the experimental data and this equation was achieved, with
values of R2 = 0.95 and 0.97, respectively, as illustrated in Fig. 6.
However, the value of the Hill exponent n at 50 °C, n = 0.18 ± 0.10,
cannot be related to that obtained under the same conditions for a
polymerization temperature of 38 °C, n = 0.77 ± 0.12 [10], because it
is lower than what is expected and presents a high error. By contrast,
the value of the Hill exponent found for 60 °C, n = 1.12 ± 0.15, is
indeed in agreement with the value found for 38 °C. However, it is
important to note that this n parameter is different from the reaction
order discussed in the previous section, and it lacks physical meaning.
On the other hand, these absorbance relationships for the fractions
obtained at 70, 80, and 90 °C cannot be correctly fitted to the Hill
function. Very poor R2 values were obtained, R2 ~ 0.5, and the n values
are not consistent between them, and their standard errors are certainly
great (n = 0.18 ± 0.20, n = 0.29 ± 0.14 and n = 0.15 ± 0.34 for
70 °C, 80 °C and 90 °C, respectively), indicating that this approach to
the kinetics of polymerization by means of UV–Vis makes no sense for
these high temperatures. Moreover, the variation in the UV–Vis spectra
of the sol fractions during the polymerization process recorded at these
higher temperatures has significant differences with respect to those
recorded at 50 and 60 °C, and the spectra are notably more complex
than those described at 38 °C, as explained above.
These results seem to indicate that there is a dissimilarity in the
pathway of NH4CN polymerization, where the oligomeric intermediates
have a different chemical nature dependent on the reaction tempera-
ture, and by extension, the formation mechanism and kinetics should be
different, as explained in the previous sections.
I. Mas, et al.
3.2. Structural properties of insoluble NH4CN polymers
Taking into account the results discussed up to this point, it seems
evident that the mechanism and kinetics to explain the polymerization
of NH4CN in water are dependent on the temperature. These differences
should also be reflected in the structural characteristics of the final
products of the reactions. Thus, a systematic description of the struc-
tural properties of the NH4CN polymers was made.
3.2.1. Elemental analysis
Fig. 7 shows the molar ratios C/N, C/H, C/O and N/O as a function
of the conversion degree and the reaction temperature for the NH4CN
polymers synthesized here. From the plot of the C/N molar ratio,
Fig. 7a), it is clearly observed that the ratio increases with the con-
version degree, indicating denitrogenation processes throughout the
reaction progress. This effect is more noticeable at higher reaction
temperatures when the polymerization is carried out at 90 °C, and the
final product contains less nitrogen than that synthesized at 50 °C, ac-
cording to previous results reported from 75 to 90 °C [12]. Thus, the
high temperatures and conversion degree favour the denitrogenation
processes, and under these conditions, lower limit conversions are
achieved. Looking at the C/H molar ratio, Fig. 7b), it is seen at 90 °C
that the increase in the conversion degree of the system leads to more
conjugated macrostructures. At the other three temperatures, the effect
is not as evident, but in general, there is an increase in the conjugation
of the system with the conversion degree, likely through dehy-
drogenation reactions. It seems that more conjugated structures are
formed at 70 °C, at medium conversion degrees. Finally, from the in-
formation proven by the C/O and N/O molar ratios, it can be seen that
an increase in the temperature favours hydrolytic and/or oxidative
reactions during the polymerization, as was reported previously [12].
In summary, the 3D plot of Fig. S2 is very enlightening, where it is
observed that the variation in composition undergoes during the
polymerization process is directly dependent on the reaction tempera-
ture: The higher temperatures enhance the denitrogenation and hy-
drolytic/oxidation process together with dehydrogenation reactions
throughout the polymerization, leading to macrostructures that are
more oxidized, conjugated and richer in carbon than in nitrogen.
3.2.2. FT-IR analysis
Fig. 8 shows a representative selection of FT-IR spectra for insoluble
NH4CN polymers synthesized at different temperatures and indicates
the conversion degree for each of them. All spectra can be divided into
four main regions: region I (3700–3000 cm−1), region II
(2275–2000 cm−1), region III (1825–1000 cm−1) and region IV centred
at 660 cm−1. The description and assignation of these bands as well as
the evolution of the nitrile groups throughout the polymerization pro-
cess have been largely described previously [2,12,16]. Therefore, we
think that it is not necessary to discuss these aspects again. However,
quantitative data for comparative proposes can be obtained from the
intensities between the peak centred at ~1645 cm−1, I1645 (assigned to
conjugated C]C, to (C]N)n structures or to a combination of the two),
and the nitrile peak centred at ~2200 cm−1, I2220. Both signals can be
used as internal indicators of the extent of reaction (EOR, %) through
the relationship EOR = [I1645/(I2220 + I1645)] × 100 [12 and internal
references]. In the upper part of Fig. 9, this relationship is represented
as a function of the conversion degree. In general, the EOR value in-
creases with the conversion degree, independent of the temperature;
however, this parameter is higher for the samples synthesized at higher
temperatures. This result is in good agreement with the compositional
analysis data discussed above. The degree of hydrolysis of the NH4CN
polymers and/or the oxygenated composition is higher for the NH4CN
polymers synthesized at higher temperatures.
Nevertheless, it is noteworthy that the evolution of the bands
centred at ~3340 and ~1645 cm−1 with the conversion degree is op-
posite for the NH4CN polymers synthesized at 50 °C and at 90 °C
7
European Polymer Journal 132 (2020) 109719
(Fig. 8). The broad band at ~3340 cm−1 can be assigned to hydro-
genated functional groups such as amines (eNH2, eNH), amides (eNH,
amide I) and hydroxyl groups (eOH). At 50 °C, the intensity of the band
at ~1645 cm−1 decreases throughout the polymerization, while the
relative intensity of the band at ~3340 cm−1 remains constant. This
same relationship is observed for those samples synthesized at 60 °C
and for those produced at 70 °C, but with a minor range of differ-
entiation (Fig. 8). It appears that the evolution of the system at 60 and
70 °C is intermediate between the process that takes place at the lowest
temperature and the highest temperature considered herein. In con-
trast, at 90 °C, the intensity of the band at ~3340 cm−1 decreases with
the conversion degree, and the band at ~1645 cm−1 remains unaltered
throughout the polymerization process. Note that all spectra were
normalized based on the more intense band for each case.
Therefore, it is also interesting to calculate the following relation-
ship [I1645/(I3340 + I1645)] × 100 as other and complementary quan-
tification of the progress of the NH4CN polymerization, making use of
the same equation employed for the EOR. The bottom part of Fig. 9
shows this new relationship, which increases with the conversion de-
gree when the NH4CN polymers are synthesized at 90 °C and decreases
when the samples are synthesized at 50 °C. Intermediate values were
calculated for 60 °C and 70 °C, with a decreasing tendency at 60 °C and
a relatively constant or light decrease for the NH4CN polymers syn-
thesized at 70 °C (Fig. 9). In addition, this relationship might help to
interpret the ratio of conjugation of these macromolecular systems
because the band at ~1645 cm−1 is related to unsaturated double
bonds and the band at ~3340 cm−1 is assigned hydrogenated func-
tions, as discussed above. Thus, higher values for this spectroscopic
parameter may indicate a greater conjugation of the macrostructure
considered. In this case, the NH4CN polymers synthesized at 90 °C may
present more conjugated macrostructures than those synthesized at
50 °C.
In addition, the shape and width of the band centred at
~3340 cm−1 can be related to the presence of –COOH and –CONH2
groups and therefore associated with hydrolysis reactions. For the
NH4CN polymers synthesized at 50 and 60 °C, it is clearly observed that
this band is broadened during the polymerization process. This effect is
also identified for the samples obtained at 70 °C, but it is not so notable.
In contrast, for the polymers produced at 90 °C, the effect is the op-
posite; at higher conversion degrees, the intensity and width of this
band are minor. Taking into account these results and the elemental
analysis discussed above, the hydrolysis process to generate eCOOH
and eCONH2 groups might be mainly during cyanide polymerization at
the lowest temperatures considered here, and other oxidation processes
that lead to more conjugated macrostructures might occur at higher
temperatures.
3.2.3. Solid-state NMR spectroscopy
To find other structural differences beyond those commented for
elemental analysis or FT-IR spectroscopy, the 13C CP MAS-NMR spectra
of a selection of NH4CN polymers at limit conversions were recorded, as
displayed in Fig. 10. No significant differences were found among the
three spectra, neither in the recently reported spectra of the samples
synthesized at 80 °C [2] nor with those obtained at 38 °C [16]. The
deconvolution of the resonances of these spectra leads to the accurate
interpretation of this complex and heterogeneous system, which was
made in detail in a recent article [2]. This exhaustive analysis indicated
the presence of several functional groups such as carbon in N-con-
taining functional groups (> C]NH, extended pyridines, pyrroles,
amides and γ- and δ-lactams), double bonds (C]C) or triple bonds
(C^N) and carbon–nitrogen single bonds (CeN). Only slight differ-
ences were found between the intensity of the resonances in the range
of 130–110 ppm. The low intensity in the spectrum of the polymer
synthetized at 50 °C could be in agreement with the minor oxidation
state of this sample, according to the data obtained by elemental ana-
lysis.
I. Mas, et al. European Polymer Journal 132 (2020) 109719

Fig. 8. FT-IR spectra of insoluble NH4CN polymers obtained from water polymerization at different temperatures. Note that all spectra are normalized based on the
more intense band, which is dependent on the polymerization temperature and the conversion degree.

Fig. 9. Dependence of both the extension of reaction (EOR) and the relationship
[I1645/(I3340 + I1645)] × 100 calculated from the FT-IR analysis on the con-
version degree of insoluble NH4CN polymers obtained using different tem- Fig. 10. CP MAS solid-state 13C NMR spectra of NH4CN polymers synthesized at
peratures. different temperatures and at limit conversions for each case.

As discussed in previous works, the scarce or null solubility of HCN
polymers in common solvents makes their proper characterization
highly difficult. Thus, alternative techniques should be applied for the
characterization of these solid materials to obtain a better under-
standing of their complex nature and the differences between them,
such as X-ray diffraction.
3.2.4. XRD powder patterns
The X-ray diffractograms of a selection of NH4CN polymers were
recorded (Fig. 11). In Table S3, the main crystallographic parameters
are detailed. All samples show a diffraction at ~27.2° and a d-spacing of
~3.27 Å. These XRD profiles are identical to those described previously
for NH4CN polymers synthesized at 80 °C with different conversion
degrees [2]. All these XRD profiles present an extraordinary similarity
with those observed for layered graphitic carbon nitrides g-C3N4, with a

8
I. Mas, et al. European Polymer Journal 132 (2020) 109719

Fig. 11. Representative XRD patterns of NH4CN polymers synthesized at dif-

ferent temperatures and at limit conversions for each case.

peak at 2θ = 27.5° related to the (0 0 2) diffraction typically found in

layered crystal structures [17,18]. These materials have been recently
reviewed due to their singular properties and wide range of applications
[18]. Our results appear to indicate the presence of graphitic-like 2D
structures in the macrostructure of the NH4CN polymers studied here.
In addition, the % of crystallinity of the samples increases when the
polymerization temperature is higher (Table S3), and the peak centre at
27.2° is also narrowed in an identical way (Fig. 11). These last results
might indicate that a higher temperature of polymerization leads to
more ordered NH4CN polymers and therefore to more thermo-
dynamically stable macrostructures.

3.2.5. Study of the insoluble residues after acid hydrolysis of the NH4CN
polymers
It is well known that the acid hydrolysis of insoluble NH4CN poly-
mers generates an important set of polar molecules with interest in
prebiotic chemistry [1,19–21]. However, few studies have been re-
ported on the insoluble residues collected after these hydrolysis con-
ditions. The resistance of the HCN polymers to this treatment may also
give an indication regarding the chemical stability of these substances,
beyond the results obtained by XRD. Fig. 12a) shows the weight per-
centage of the insoluble residues collected after acid hydrolysis for
samples of NH4CN polymers synthesized at all temperatures under
study for longer reaction times when a limit conversion is achieved. It is
observed that the amount of insoluble hydrolysed residues increased as
the polymerization temperature increased. This means that NH4CN
polymers synthesized at higher temperatures appear to be more stable
against acid hydrolysis or at least yield a minor amount of soluble or-
ganic materials.
In the same figure, compositional data of these insoluble residues
after acid hydrolysis indicate that these samples are more oxidized than
unhydrolysed samples due basically to a loss of nitrogen, regardless of
polymerization temperature [Fig. 12b)]. The samples synthesized at
90 °C, although they are initially the most oxidized, are the least oxi-
dized once hydrolysed [Fig. 12c)]. This result was confirmed by a new
FT-IR analysis. As expected, the spectra of these hydrolysed residues do
not show the characteristic peak of the NH4CN polymers at
~2200 cm−1 related to nitrile groups, and the band centred at
~3340 cm−1 undergoes a shift to 3302 cm−1. Additionally, this band is
clearly broadened due to hydrolysis of nitrile groups to carboxylic acids
(please compare the four regions described for the FT-IR spectra of
insoluble NH4CN polymers shown in Fig. 8 with those presented in
Fig. 12. a) Weight of the insoluble residues collected after acid hydrolysis of
NH4CN polymers synthesized at different temperatures and at limit conver-
sions. This percentage was calculated as follows: (mg of insoluble hydrolysed
residue/mg of insoluble NH4CN polymers) × 100. The temperature indicated in
the x-axis corresponds to the polymerization temperature used for the syntheses
of the NH4CN polymers. b) and c) Elemental analysis data of the insoluble re-
sidues collected after acid hydrolysis of these same polymers.
Fig. 13, where only three regions can be observed). Taking into account
the FT-IR spectra of the insoluble hydrolysed residues of NH4CN poly-
mers (Fig. 13) and those of the respective unhydrolysed samples
(Fig. 8), it seems that the main macrostructure remains inalterable, and
only the sensitive functional groups to be hydrolysed are subjected to
the corresponding reactions.
In summary, the temperature has a notable effect on the structure of
the insoluble NH4CN polymers. The polymers synthesized at 90 °C
present structures that are more oxidised, more conjugated, more
crystalline and ordered and more stable against acid hydrolysis than
those polymers synthesized at lower temperatures.
3.3. Some mechanistic, structural and practical aspects about the aqueous
cyanide polymerization
In this section, a series of clues for the elucidation of the reaction
pathways for the production of the insoluble cyanide polymers are
suggested, based on the classic experiments made by Ferris and co-

9
I. Mas, et al. European Polymer Journal 132 (2020) 109719

the chemical transformations that may take place during HCN oligo-
merization, and they found that HCN undergoes a rapid, essentially
irreversible, condensation to DAMN to give oligomeric products [23].
They postulate that redox reactions occur during this process to give
reduced HCN oligomers and diiminosuccinitrile (DISN). These dinitriles
are easily converted to the corresponding hydrolysis products and can
also react among themselves, as has been described in a recent study
based on aqueous DAMN polymerization, where a general picture is
provided; please see Scheme 2 in reference [2]. Therefore, DISN hy-
drolyses to oxalic acid and urea, while DAMN can give the monoamide
of the aminomalononitrile and one equivalent of cyanide or aminoa-
cetonitrile and the monoamide of cyanogen. The monoamide of cya-
nogen may cleave as cyanogen does to yield one equivalent of cyanide;
however, it appears unlikely that a second equivalent of cyanide will be
formed by either reaction pathway, according to Ferris and Edelson
[23]. The monoamide of AMN is known to hydrolyse to the diamide,
and it does not eliminate cyanide, as indicated in Scheme 1. This
Fig. 13. FT-IR spectra of insoluble residues collected after acid hydrolysis of a
selection of insoluble NH4CN polymers synthesized at different temperatures scheme shows that a significant amount of carboxylic acids and amides
and at limit conversions. and other molecular species are formed during HCN polymerization in
water. The production of these carboxylate compounds (carboxylic
acids and amides) by hydrolysis and decyanation are more favourable
workers and other recently reported results. On the other hand, it is
at high temperatures, due to the thermal activation of the system. These
significant that computational studies have indicated the possible ex-
oxidised molecules might lead to other secondary and/or crossing re-
istence of 678 tetrameric structures generated from HCN without con-
actions beyond those shown in Scheme 2 and of the hypothetical
sidering the role of the water [22]. Therefore, taking in account that the
pathways detailed in reference [2], increasing the complexity of the
cyanide polymerization mechanisms seem to be directly dependent on
aqueous cyanide polymerization mechanism. This assumption also
the temperature, such as is indicated above, only some suggestions
might explain the lower conversion obtained for the insoluble NH4CN
about the pathways of reaction are discussed, an only few plots are
polymers at the higher temperatures; and it also might be related on the
shown in an attempt to understand the wide and complex chemical
fact that the UV–Vis spectra of the sol fractions from the higher tem-
space of HCN. Starting from this point, the potential role of cyanide
peratures are more complex than those obtained at the lower tem-
polymers as multifunctional materials and their implications in pre-
peratures. Thus, if the number of possible monomers and oxidised
biotic chemistry are discussed.
molecules which can potentially promote the oligomerization/poly-
Several studies have tried to analyse the catalytic effects on the
merization is increased, the collected amount of the insoluble polymers
condensation reaction of HCN to oligomers. In the first step, HCN
is decreased. This result is due to the increasing of possible reactions in
condenses to form a dimer (iminoacetonitrile), trimer (aminomalono-
the system which might produce a larger diversity of soluble oligomers/
nitrile, AMN) and tetramer (DAMN). One or more of these simple HCN
polymers. In addition, it is important to remember the kinetic study of
derivatives polymerize to yield a complex of substances and may also
Schwartz and Goverde [15], where they demonstrated that different
undergo hydrolytic and/or redox reactions, as indicated in Scheme 1.
cyanohydrin compounds markedly accelerate the rate of HCN oligo-
At this point, if it is difficult to know with certainty the key monomer
merization, both in homogeneous solution as well as in the frozen
that originates the growing chains, it can be truly more problematic to
aqueous state. All these results suggest that hydroxylated compounds,
elucidate what compound acts as the catalyst during this reaction.
generated from hydrolysis and/or oxidation reactions, can have a cat-
However, all the studies coincide in pointing to AMN or DAMN as the
alytic effect during the polymerization process. At the higher tem-
true monomers that give rise to the growth of the polymer chains.
peratures considered here, the hydrolysis and/or oxidation reactions
Therefore, as an example in Scheme 2, a general picture of the poly-
seem highly probable considering the structural data reported in the
merization reaction in aqueous medium is presented. Here, it is possible
previous sections, and the discussion indicated above. Since the auto-
to distinguish two polymerization routes. On the one hand, one route is
catalytic behaviour must be considered at the higher temperatures
based on the formation of a linear polyimine through the decomposi-
studied, some of the oxidised molecules specified above must be the key
tion step of the trimer AMN to give a carbene with the elimination of
in the autocatalytic process. However, due to the complexity of the
hydrogen cyanide. It seems more likely that this polyimine, formulated
system and the current information (computational as well as analy-
here with an oligomeric formula of C12N12H12, can yield the different
tical/spectroscopic), it is very difficult to indicate which of them can be
heterocyclic macrostructures indicated in this scheme according to the
the kingpin in the autocatalytic behaviour at the higher temperatures.
mechanism explained in detail in a recent work [2]. In addition, in this
Moreover, other possibilities also exist; for example, polymeric pro-
study, the hydrolysis of polyamine and subsequent intramolecular cy-
ducts formed during the precipitating polymerization could act as cat-
clization are postulated to give a new family of oxygenated heterocycles
alysts. In this sense, the autocatalytic character of HCN polymers is
onto the polymeric chains. On the other hand, Thissen and co-workers
known, and it has been demonstrated experimentally by seeding a to-
have proposed a new mechanism for AMN polymerization from aqu-
luene solution of HCN with a dark HCN polymer and finding that it
eous solutions, giving in this case polymeric films, as indicated in this
promotes the formation of a new polymer [internal references in 12].
scheme [8]. They suggest the formation of a linear polyamine,
At this point, the results presented herein offer, on the one hand,
C12N12H12, by a polyaddition between amine and cyano groups, which
that high temperatures lead to highly conjugated and oxidised and re-
evolves to a polyaminoimidazole; they also propose its hydrolysis to
latively largely ordered HCN-derived polymeric structures. It is also
give a new macrostructure with carbonyl groups in the imidazole rings,
likely that these high temperatures might lead to changes in the mor-
C12N9H3O3, according to experimental compositional data. Logically,
phology, size and density of the final cyanide polymerization products
the hydrolysis reaction of polyamine must be considered, as well as
(preliminary results of further work in progress are in agreement with
other hypothetical macrostructures such as those presented in this
this assumption). And on the other hand, the temperature has a sig-
scheme.
nificant influence in the kinetics of the production of HCN-derived
Returning to Scheme 1, Ferris and Edelson scrutinized in high detail
polymers and subsequently in the mechanistic pathways. The great

10
I. Mas, et al. European Polymer Journal 132 (2020) 109719

Scheme 1. Oligomerization of cyanide and hydrolysis reactions according to pioneering studies by Ferris and co-workers [14,22].

complexity of the cyanide polymerization pathways in aqueous en- The confusion is still greater when the nature of the precursors that lead
vironment is well-known, but here we demonstrate and for the first to this autocatalytic behaviour is unknown. However, in spite of these
time, that this complexity is greater than expected, since the mechan- newly revealed open questions indicated here, some notable practical
isms of HCN-derived polymer production are temperature dependent. suggestions can be made based on the new structural data obtained: i)

Scheme 2. Hypothetical pathways for the formation of HCN polymer from AMN according to recent works in the literature [2,8].

11
I. Mas, et al.
the versatility of the HCN-derived polymers synthesis allows one to
tune the properties of the polymers by a correct selection of the reaction
conditions, such as temperature and time; ii) recently this polymeric
system has been compared to graphitic carbonitrides due to the partial
presence of graphite-like 2D structures in NH4CN and DAMN polymers
[2]. The high temperature favours the arrangement in graphite-like 2D
structures, such as was shown by XRD. This result, and the more con-
jugated structures of the polymers obtained at the higher temperatures,
encourage us to study the potential applications of these polymers as
new multifunctional materials in analogy to the well-known g-C3N4
graphitic carbonitrides [18]; iii) the fine-tuning of the textural prop-
erties by changes in the morphology, size or density, prompted by the
temperature conditions, can lead to the obtention of HCN-derived
polymeric nanoparticles which can be incorporated in other polymeric
matrices which could have a relevant impact in the field of polymer
composites, as was previously proposed [2]; iv) the thermal conditions
might also be able to tune the properties of the HCN-derived polymeric
coatings, currently promising materials with potential biomedical ap-
plications [4,5]; v) the HCN is a ubiquitous molecule in the Universe
and it is considered as a preferential prebiotic reagent since the HCN
polymers are proposed as main prebiotic precursors of important bio-
molecules (see reference [1] and the references therein). In addition,
the HCN polymers are considered the oldest organic materials in the
Solar System. Now, it is revealed that they provide potential properties
as semiconductors and catalysts and subsequently they will likely have
an important role in the development of new reactions. Thus, the HCN-
derived polymers may lead to the discovery of new unexplored horizons
in prebiotic chemistry, beyond the traditional ways marked by Oró's
synthesis of adenine [24].
4. Conclusions
It has been demonstrated that the temperature has a significant
effect on NH4CN polymerization. The fit to phenomenological kinetic
models, autocatalytic or nth order, is conditioned by the reaction
temperature. Moreover, this result is reflected in good agreement
through the structural features and properties of the insoluble NH4CN
polymers synthesized. Therefore, an autocatalytic mechanism seems to
prevail at higher temperatures, and the respective insoluble polymers
present highly oxidized, conjugated and ordered macrostructures;
therefore, they are more thermodynamically stable. In contrast, an nth-
order kinetic model is followed for these precipitation polymerizations
when they react at medium temperatures, and in this case, the corre-
sponding polymeric materials are more labile and disordered, according
to both XRD and chemical stability measurements.
For the first time, a reliable value for the activation energy of cya-
nide polymerization, between 50 and 90 °C, has been obtained from the
initial polymerization rate, where the polymerization is chemically
controlled. The empirical model proposed herein allows an excellent
description of the two regions, chemical- and diffusion-controlled, that
characterize the kinetic behaviour of this extraordinarily complex
polymerization reaction, which presents diffusion limitations. This ap-
proach based on the Hill equation is simple, easy to use and in very
good agreement with the experimental data, and it could be applied to
other experimental polymerization conditions. Moreover, the descrip-
tion of the kinetically and chemically controlled stages and the limiting
diffusion conversions have been accurately described from 38 to 90 °C.
From an industrial standpoint for process modelling and optimiza-
tion, this methodology is usually preferred. However, it is important to
note that the reactions carried out herein are not stirred to favour
precipitation processes. Thus, new experiments must be performed to
elucidate the full role of the diffusion stage when NH4CN polymeriza-
tions are driven by a stirring method. All the results shown, both the
kinetic and the structural and spectroscopic data, may be very useful in
designing new materials dependent on the desired applications and in
beginning to understand the real role of cyanide polymerization in
12
European Polymer Journal 132 (2020) 109719
prebiotic chemistry and astrobiology.
CRediT authorship contribution statement
Itziar Mas: Validation, Formal analysis, Investigation. José L. de la
Fuente: Conceptualization, Methodology, Formal analysis, Writing -
original draft, Writing - review & editing. Marta Ruiz-Bermejo:
Conceptualization, Methodology, Validation, Formal analysis,
Resources, Writing - original draft, Writing - review & editing,
Supervision, Funding acquisition.
Declaration of Competing Interest
The author(s) declare no competing interests.
Acknowledgements
The authors used the research facilities of the Centro de
Astrobiología (CAB) and were supported by the Instituto Nacional de
Técnica Aeroespacial “Esteban Terradas” (INTA), by the project
ESP2017-89053-C2-2-P from the Spanish Ministerio de Ciencia,
Innovación y Universidades and by the Spanish State Research Agency
(AEI) project MDM-2017-0737 Centro de Astrobiología (CSIC-INTA),
Unidad de Excelencia María de Maeztu. Additionally, the authors are
grateful to Mª Teresa Fernández for performing the FT-IR spectra and
XRD measurements and to David Hochberg for the detailed revision of
the manuscript.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time due to technical or time limitations.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.eurpolymj.2020.109719.
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