Chemical Engineering Science 152 (2016) 248–254

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Chemical Engineering Science

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

First investigation of modified poly(2-vinyl-4,4-dimethylazlactone)s as

kinetic hydrate inhibitors
Lilian H.S. Ree a, Malcolm A. Kelland a,n, Peter J. Roth b,c, Rhiannon Batchelor c
a
Department of Mathematics and Natural Science, Faculty of Science and Technology, University of Stavanger, N-4036 Stavanger, Norway
b
Department of Chemistry, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford, Surrey GU2 7XH, United Kingdom
c
Centre for Advanced Macromolecular Design, University of New South Wales, Sydney, Australia

H I G H L I G H T S

A series of amine derivatives of poly(2-vinyl-4,4-dimethylazlactone)s has been synthesized.

The polymers have been investigated as kinetic hydrate inhibitors for the first time.

Performance increased with decreasing molecular weight down to 1845 mol/g.

The best performance was for the n-propylamine derivative.

art ic l e i nf o a b s t r a c t

Article history: A series of polymers of 2-vinyl-4,4-dimethylazlactone (VDMA) of varying molecular weights modified
Received 16 March 2016 with small organic amines have been synthesized. Their performance as kinetic hydrate inhibitors (KHIs)
Received in revised form has been investigated in high pressure steel rocking cells using a Structure II-forming synthetic hydro-
19 May 2016
carbon gas mixture. It was found that the PVDMA polymer with the lowest molecular weight (Mn
Accepted 12 June 2016
¼1845 g/mole by 1H NMR) performed the best. It was also found that the n-propylamine derivative
Available online 15 June 2016
performed the best of the amine derivatives. The cloud point of this polymer derivative was found to be
Keywords: lower than ambient temperature, which is considered too low for practical oilfield applications. However,
Petroleum high cloud point PVDMA derivatives such as the ethylamine or pyrrolidine derivatives still gave rea-
Low dosage hydrate inhibitor
sonable KHI performance. The KHI performance of the n-propylamine derivative of PVDMA-I was tested
Kinetic hydrate inhibitor
at different concentrations in the range 1000–7000 ppm. It was found that the performance improved as
Hydrate
Polymers the polymer concentration was increased.
Kinetics & 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Gas hydrate plugging is a major flow assurance issue to con-
sider in the oil and gas industry, particularly for flow lines in
subsea and cold climate situations (Carroll, 2009; Makogon, 1997;
Sloan and Koh, 2008). One of the methods to combat this problem
is the use of kinetic hydrate inhibitors (KHIs) (Kelland, 2006;
Kelland, 2011; Perrin et al., 2013). KHIs are one class of low dosage
hydrate inhibitors (LDHIs) which, as the name implies, are added
at low concentrations in the order of 0.5–2 wt.% as formulations in
solvents. KHIs are often a mixture of chemicals but always with
one or more water-soluble polymers as the main active in-
gredients. Synergists may be added, which may include other
polymers or non-polymeric chemicals including the solvent
(s) used in the formulation. Many polymers have been investigated
n
Corresponding author.
for their efficacy as KHIs but only a few have been commercialized.
This includes polymers based on the monomers N-vinyl pyrroli-
done, N-vinyl caprolactam (VCap) and N-isopropylmethacrylamide
(NIPMAM) as well as hyperbranched poly(ester amide)s. One of
the field compatibility issues with KHI polymers is that they often
have limited solubility in produced water especially at high tem-
peratures and salinities (Kelland, 2014). Above a certain tem-
perature called the cloud point (TCl) the polymer will often phase
separate, giving a cloudy solution. Further heating to usually an
incrementally higher temperature (TDp) can lead to precipitation of
the polymer, which may then deposit and build up in the flow line
near the injector site. Operator and service companies would
consider this detrimental as the polymer is then apparently un-
available in the water phase for carrying out kinetic hydrate in-
hibition. Although field cases exist where a KHI polymer has been
injected into well stream temperatures above the cloud and de-
position point, and successfully used to prevent hydrate formation,
most operators prefer to avoid this complication by using a

http://dx.doi.org/10.1016/j.ces.2016.06.031
0009-2509/& 2016 Elsevier Ltd. All rights reserved.
 L.H.S. Ree et al. / Chemical Engineering Science 152 (2016) 248–254 249

product that will remain water-soluble or at worst water-dis-

persible at the well head temperature.
Poly(N-vinyl caprolactam) (PVCap) and poly(N-isopropylmet-
hacrylamide) (PNIPMAM) have cloud points around 30–45 °C de-
pending on the method of manufacture. This is often too low for
injection at the well head temperature. One way to overcome this
problem is to add chemicals that often also act as synergists, to
raise the deposition point of the KHI formulation when injected
(Kelland, 2014). Another method is to copolymerize the active
monomers with a more hydrophilic comonomer. For example,
VCap or NIPMAM copolymerize in a 1:1 M ratio with N-methyl-N-
vinyl acetamide (VIMA) with optimized molecular weight dis-
tributions have been shown to give similar or superior perfor-
mance KHIs to the homopolymers but with significantly higher
cloud and deposition point temperatures (Colle et al., 1999; Talley
and Mitchell, 1998). Another method is to build into the active
monomer a more hydrophilic functional group so that the new
homopolymer will be water-soluble at higher temperatures than
the unmodified polymer. An example of this is the use of di-
methylhydrazido groups instead of isopropylamido groups in
substituted acrylamide monomers (Fig. 1) (Mady and Kelland,
2014). The extra nitrogen atom in the hydrazido group confers
a greater hydrophilicity on the monomer than just one nitrogen
atom from an amide group. Thus, poly(dimethylhy-
Fig. 2. Alkylated AMPs polymers, where R1 is an alkyl tail of 1–6 carbon atoms and
drazidoacrylamide) has no cloud point in water as a 1 wt.% aqu-
R2 is H or CH3.
eous solution at any temperature up to 100 °C. This homopolymer
or copolymers with NIPMAM or VCap are still very active KHIs
with improved cloud points compared to PVCap or PNIPMAM
(Mady and Kelland, 2015).
A related example of modifying a monomer to raise the cloud
point of its polymers is the alkylated polyacrylamidopropylsulfonates
(alkylated polyAMPS) (Fig. 2). (Peiffer et al., 1999) A hydrophobic
pendant alkyl group alone would not give a water-soluble polymer
but incorporation of a hydrophilic sulfonate group made this polymer
class water-soluble as long as the alkyl chains R1 and R2 were not too
large. Conversely, the AMPS homopolymer alone is a poor KHI, but it
was found that the addition of a hydrophobic tail between the amide
and the sulfonic acid group increased the performance of the poly-
mer. The optimum size of the tail R1 was 5 carbon atoms long. A
homopolymer of this monomer gave a KHI performance similar to Fig. 3. Poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) (left) and ring-closed poly-
PVCap in a high pressure natural gas mini-loop. vinyloxazolines, R¼ H or CH3 (right).
We were initially interested in poly(2-vinyl-4,4-dimethyla-
zlactone) (PVDMA) as the azlactone pendant ring resembled the
oxazoline ring that had been investigated earlier as a functional
groups for KHI polymers in polyvinyloxazolines (Fig. 3) (Reyes
et al., 2013; Colle et al., 1996). The monomer 2-vinyl-4,4-di-
methylazlactone is commercially available but not on an industrial
scale.
However, PVDMA is not water-soluble as the homopolymer, al-
though it was known that PVDMA hydrolyzes to give poly(N-acry-
loyl-2-methylalanine) (PAMA) with both pendant dimethyl groups
and a carboxylate group (Fig. 4) (Gardner et al., 2012). The resem- Fig. 4. Reaction scheme for hydrolysis of poly(2-vinyl-4,4-dimethylazlactone)
blance of PAMA to the alkylated AMPS polymers described earlier is (PVDMA) to the sodium salt of poly(N-acryloyl-2-methylalanine) (PAMA).

apparent. Therefore, we were interested in investigating PAMA as a

Fig. 1. Structures of polyIPAM, polyIPMAM and the hydrazine-based analogs poly
(N,N-dimethyhydrazidoacrylamide derivatives R ¼ H or CH3.
KHI. Since the size of the 2,2-dimethyl hydrophobic group was re-
latively small we expected the KHI performance to be low, and so
we sought ways to incorporate larger hydrophobic groups into the
polymer. One method is to begin with a 2-vinyl-4,4-dialkylazlactone
monomer where the alkyl groups are larger than methyl. However,
so far we have not explored this route. Instead, we chose a route
explored already by some of us by incorporating hydrophobic
pendant groups through postpolymerization modification of
PVDMA with primary or secondary amines (Fig. 5). This ring-
opening addition reaction proceeds quantitatively under mild
250 L.H.S. Ree et al. / Chemical Engineering Science 152 (2016) 248–254

2.2. Hydrolysis of PVDMA

PVDMA-II was hydrolyzed following a procedure known from the

Fig. 5. Reaction of poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) with primary or
secondary amines.
conditions and produces acrylamide polymers with pendant alkyl
or dialkylamide groups (Heilmann et al., 2001; Ho et al., 2012).
Compared to the related poly(N-alkylacrylamide)s and poly(N,N-
dialkylacrylamide)s, the PVDMA-derived species feature a bisamide
structure with the introduced alkyl groups further away from the
polyvinyl backbone and therefore with greater degrees of rotational
and vibrational freedom (entropy). As the postpolymerization
modification of PVDMA occurs at the pendant groups, all daughter
polymers derived from one reactive precursor feature identical
degrees of polymerization. This synthetic strategy is therefore ideal
to study structure–property relationships of polymer series with the
same degree of polymerization. Additionally, several PVDMA-de-
rived bisamide species were recently shown to have tunable cloud
points in aqueous solution (Zhu et al., 2013; Quek et al., 2013; Pei
et al., 2015). As such, PVDMA presented a promising reactive plat-
form to investigate the KHI performance of polyPAMA as well as a
range of novel PVDMA-derived bisamides of various degrees of
polymerization in high pressure rocking cells with a natural gas
mixture.
2. Experimental
2.1. Chemicals
All chemicals and solvents were purchased from VWR and
Sigma-Aldrich and were used without further purification.
Four PVDMA precursors of different molecular weight were
prepared by the RAFT process following a literature procedure
(Moad et al., 2012; Zhu et al., 2013). Briefly, VDMA monomer, RAFT
agent benzylpropyltrithiocarbonate, acetonitrile, and 4,4′-azobisi-
sobutyronitrile as radical initiator were combined and heated to
70 °C under inert atmosphere for 7 h. PVDMA samples I–IV were
prepared by varying the ratio of monomer to chain transfer agent
(see Table 1). Polymers were isolated by repeated precipitation
into methanol. Monomer conversions ranged between 44–80%.
Polymer molecular weights were calculated from monomer con-
version determined by 1H NMR spectroscopy. Results are given in
Table 1.
Table 1
Molecular weight of the provided polymers.
Polymer Target Degree of Actual Degree of Number Average
Polymerization Polymerizationa Theoretical Mole-
cular Weight [g/
mol]a
PVDMA-I 15 11 1845
PVDMA-II 20 16 2450
PVDMA-III 80 51 7350
PVDMA-IV 200 87 12,400
a
calculated from monomer conversion determined by 1H NMR spectroscopy.
literature (Messman et al., 2009). In a typical reaction PVDMA-II
(97.5 mg, 0.70 mmol) was added to a round bottom flask. The
polymer was dissolved in THF (3.5 ml), and aqueous NaOH (1 M,
0.35 mL, 0.5 eq) was added. The solution was stirred at room
temperature for 15 min before additional aqueous NaOH (1 M,
0.35 mL, 0.5 eq) was added. The solution was stirred at room
temperature for 30 min. Then the solvent was removed in vacuo.
2.3. Modification of PVDMA with different amines
The VDMA polymers of different molecular weight were modified
using different low molecular weight amines by following a proce-
dure known from the literature (Zhu et al., 2013). The example
shown here is for making the isopropylamine derivative of PVDMA.
PVDMA (0.150 g, 1.08 mmol of monomer units) was dissolved in DMF
(4.3 ml) and acrylamide (0.008 g, 0.11 mmol) was added. DMF
(2.3 ml) and isopropylamine (0.191 g, 3.23 mmol, 3.0 eq) were mixed
in a separate vial, and then added to the polymer solution. The re-
action mixture was stirred at room temperature overnight. The
polymer was precipitated in diethyl ether twice, and was then dried
in vacuo. The different modified polymers were isolated in high yields
(75–98%). Fig. 6 summarizes all the amide derivatives of PVDMA that
were synthesized using this method.
2.4. Determination of cloud point (TCl)
A 2500 ppm solution of polymer in deionized water was
carefully heated at about 2 °C/min while making visual observa-
tions throughout. The temperature at which the first sign of haze
in the solution was observed was determined as the cloud point
(TCl). (Kjøniksen, et al., 2005). The test was repeated for
reproducibility.
2.5. High pressure KHI experimental methods
Performance testing of the modified VDMA polymers as KHIs
was conducted in a high pressure gas hydrate rocker rig experi-
ment as previously described by our research group (Chua and
Kelland, 2012). The equipment was manufactured and supplied by
PSL Systemtechnik, Germany (7) and consists of five 40 mL high
pressure steel rocking cells each containing a steel ball. The cells
are positioned in a cooling bath during the experiments (Fig. 7). A
standard synthetic natural gas mixture (SNG) known to pre-
ferentially form Structure II gas hydrates was used in the experi-
ments. The gas composition is given in Table 2.
The constant cooling KHI performance test procedure was as
follows:
1. Each cell was filled with 20 mL of deionized water in which
the sample had been dissolved to the desired concentration.
2. Air in the cells was removed by applying vacuum, then filling
the cells with SNG to 3–5 bar. The cells were depressurized
before a repeated step of vacuum was applied.
3. The cells were pressurized to approximately 76 bar with
SNG.
4. The cells were rocked at 20 rocks per minute at an angle of
40° while they were cooled from 20.5 °C to 2.0 °C at a rate of
1.0 °C/h.
5. The pressure and temperature for each individual cell, and
the temperature of the cooling bath were logged on a local
computer.
Fig. 8 shows an example of the results from a KHI experiment
done under constant cooling conditions, where pressure and
temperature are plotted against time for each cell. A pressure drop
 L.H.S. Ree et al. / Chemical Engineering Science 152 (2016) 248–254 251

Fig. 6. Amide derivatives of PVDMA synthesized. Top row, left to right: methyl, ethyl, iso-propyl, n.-propyl. Bottom row, left to right: sec-butyl, dimethyl, diethyl and
pyrroldinyl.

Fig. 7. The high pressure rocker rig with the five steel rocking cells positioned in
the cooling bath.
Fig. 8. Example of pressure and temperature data versus time for five cells in a
standard constant cooling KHI experiment. Cell 1 contained PVDMA-II modified
with isopropyl amine, while cells 2–5 contained PVDMA-III modified with
pyrrolidine.

Table 2
Composition of synthetic natural gas (SNG) used in
the experiments.

Component mole%

Methane 80.67
Ethane 10.20
Propane 4.90
iso-Butane 1.53
n-Butane 0.76
N2 0.10
CO2 1.84

of approximately 2 bar can be seen in the beginning of each ex-

periment as gas dissolves in the aqueous phase. Because each cell
is a closed system during the test, a linear pressure decrease is
seen as the temperature is reduced. The first deviation from this Fig. 9. Determination of To and Ta after a standard constant cooling experiment.
252 L.H.S. Ree et al. / Chemical Engineering Science 152 (2016) 248–254

linear pressure decrease is determined as the observed macro- Table 4

scopic onset temperature for hydrate formation, To. Nucleation Results from constant cooling KHI experiments of modified PVDMA polymers at
2500 ppm.
might have occurred earlier on an undetectable scale (Chen, et al.,
2010; Qin et al., 2015). A rapid pressure decrease is seen at some Entry Amine Polymer To(av) Ta(av) To(av) – Ta(av)
time after the initial hydrate formation temperature, which in- [°C] [°C] [°C]
dicates that hydrates are growing rapidly. The temperature at
which the hydrate growth is at its most rapid, Ta, is determined at 1 – No polymer 17.4 16.0 1.4
2 Dimethylamine PVDMA-III 15.2 14.4 0.8
the steepest part of the graph. Fig. 9 shows the pressure (P1) and 3 Ethylamine PVDMA-I 12.6 12.2 0.4
temperature (T1) for cell 1, and how To and Ta was determined for 4 Ethylamine PVDMA-II 11.9 11.4 0.5
the polymer solution in this cell. For each polymer 8–10 standard 5 Ethylamine PVDMA-III 12.9 12.4 0.5
cooling tests were carried out. It was found that none of the cells 6 n-Propylamine PVDMA-I 10.1 9.7 0.4
7 Isopropylamine PVDMA-I 10.7 10.3 0.4
gave any systematic errors that lead to consistently better or worse
8 Isopropylamine PVDMA-II 11.1 10.6 0.5
results than the other cells. As the To value refers to the first de- 9 Isopropylamine PVDMA-III 14.4 13.8 0.6
tection of hydrate formation, after which crystal growth can po- 10 Isopropylamine PVDMA-IV 14.0 13.5 0.5
tentially lead to hydrate plugging, this is considered the most 11 Sec-Butylamine PVDMA-I 12.4 12.2 0.2
important of the two temperature parameters. The difference be- 12 Sec-Butylamine PVDMA-III 16.5 15.9 0.6
13 Pyrrolidine PVDMA-I 12.2 11.9 0.3
tween the To and Ta values gives some indication of the ability of 14 Pyrrolidine PVDMA-II 13.7 13.2 0.5
the additive to retard the gas hydrate crystal growth process al- 15 Pyrrolidine PVDMA-III 13.3 12.6 0.7
though the onset temperature has to be considered when com- 16 Diethylaminea PVDMA-III N/A N/A N/A
paring hydrate growth rates. a
Not soluble in water.

amines in order to increase the hydrophobic portion of the poly-

3. Results and discussion
3.1. KHI performance of hydrolyzed PVDMA
As PVDMA homopolymer is not soluble in water, the polymer
was hydrolyzed as shown in Fig. 4 prior to testing to make it
water-soluble. The results from the KHI performance test of PAMA-
II made from hydrolyzing PVDMA-II are presented in Table 3 and
compared to the results for deionized water (no polymer).
As can be seen from Table 3 the performance of PAMA-II at
2500 ppm was quite similar to the performance of pure, deionized
water. This suggests that PAMA-II is not able to kinetically inhibit
the formation of gas hydrates. In comparison we carried out ex-
periments at the same conditions and the same equipment on a
poly(N-vinyl caprolactam) (PVCap) (Mw ¼ 4092 g/mole), as well as
a low molecular weight poly(N-isopropylacrylamide) (PNIPAM) (
Mw ¼ 7353 g/mole) synthesized in our own laboratory (Mady and
Kelland, 2014, 2015). Neither polymerization procedure or the final
molecular weight distribution had been optimized for best per-
formance but both gave reasonably low To values and thus rea-
sonably good performances as KHIs compared to the negligible
KHI effect of PAMA-II. Commercial KHI solutions that contain
polymers such as PVCap give lower To values in our laboratory but
we have chosen to compare PVCap and PNIPAM made in un-
optimized processes in our laboratories as a better comparison to
the KHI activity of the new PVDMA-based polymers which are also
unoptimized (Mady and Kelland, 2014; Reyes and Kelland, 2013).
mers. After modification the KHI performance testing was carried
out in high-pressure natural gas hydrate constant cooling rocking
cells experiments. Table 4 summarizes the average onset (To) and
fast hydrate formation temperatures (Ta) from 8–10 experiments.
The experiments with no additive (i.e. pure deionized water, entry
1 in Table 3) are again included for comparison. The same data are
presented in Fig. 10 to show the data scattering. Although there is
a lot of data here, we thought it helpful to place all the results on
one graph so any trends can be determined visually. In order to
make Fig. 10 easier to read all data corresponding to the same
PVDMA has the same shaped marker. The markers with similar
color refers to PVDMAs modified with the same amine. The die-
thylamine derivative of PVDMA-III (entry 16 in Table 4) was found
to be insoluble in water, hence, the performance of this derivative
was not tested.
As the To value refers to the first detection of hydrate formation
in the system, this temperature is considered the most important
one for evaluating the performance of a KHI. As can be seen from
Table 4 the difference between To and Ta is low for all the modified
PVDMAs tested, indicating that the polymers do not retard the gas
hydrate crystal growth process to a large extent.
As can be seen from Fig. 10 the derivatives of the lowest

3.2. Performance comparison of the different modified PVDMAs

As PAMA-II failed to show any KHI performance we in-

vestigated modified versions of the polymer by reacting PVDMA of
varying molecular weights with several low molecular weight

Table 3
Average onset (To) and rapid hydrate formation (Ta) temperatures for deionized
water, and hydrolyzed PVDMA-II, PVCap, PNIPAM at 2500 ppm.

Polymer Concentration [ppm] To(av) [°C] Ta(av) [°C] To(av) – Ta(av) [°C]

No polymer – 17.4 16.0 1.4

PAMA-II 2500a 17.0 15.8 1.2 Fig. 10. Onset (To) and rapid hydrate formation (Ta) temperatures for KHI tests at
PVCap 4k 2500 10.6 9.1 1.5 2500 ppm for all modified PVDMAs. The amine name corresponds to amine used to
PNIPAM 7k 2500 10.9 7.5 3.4 modify polymer. Number –i corresponds to which molecular weight PVDMA
polymer was modified, i.e. PVDMA-i. (For interpretation of the references to color
a
Average of three results. in this figure, the reader is referred to the web version of this article.)
 L.H.S. Ree et al. / Chemical Engineering Science 152 (2016) 248–254
Fig. 11. Results from the KHI performance testing of amine-modified versions of
PVDMA-I.
molecular weight polymer (PVDMA-I) generally gave better per-
formance than the related derivatives of the higher molecular
weight polymers. This is in accordance with earlier findings for
other polymer types (Kelland, 2006, 2011).
Fig. 11 shows onset (To) and rapid hydrate growth (Ta) tem-
peratures for all the modified polymers based on PVDMA-I, and
Table 5 summarizes the cloud points (TCl) of these derivatives. The
corresponding derivatives of the higher molecular weight VDMA
polymers are expected to give lower TCl than what is presented in
Table 5.
The cloud points are in good agreement with a previous study
on aqueous solubility of PVDMA-derived bis-amide species, taking
into account that cloud points of these polymers decrease with
increasing degree of polymerization (Zhu et al., 2013). Notably,
Table 5 includes two cloud points that had not previously been
reported – those of the sec-butylamine and pyrrolidine-modified
species. Although both amines feature four carbon atoms, the
pyrrolidine-functional polymer was found to be more water so-
luble with no cloud point measured upon heating to 95 °C. This
solubility was attributed to a reduced flexibility of the cyclic side
groups imposing less steric hindrance for water to hydrogen bond
to the amide moieties effectively making the polymer more hy-
drophilic and in agreement with poly(N-alkylacrylamide)s (Zhu
et al., 2013; Aseyev et al., 2011).
The derivatives that show the best performance as KHIs are the
n-propylamine and iso-propylamine derivatives (Fig. 6). The n-
propylamine derivative of PVDMA-I performed slightly better than
the iso-propylamine derivative as a KHI. A t-test analysis gave the
result p ¼0.01, indicating that the difference between the deriva-
tives is significant (p-value o0.05) (Myers et al., 2007). Previous
work on N-alkyl-N-vinyl formamide copolymers also showed that
the n-propyl derivatives performed better as KHIs than the iso-
propyl derivatives (Kelland et al., 2015). As can be seen from Ta-
ble 5 these two derivatives have cloud points (TCl) lower than
room temperature, but are not insoluble at 0 °C. The exact TCl value
Table 5
Cloud points (TCl) of the amine-modified derivatives of
PVDMA-I measured for 2500 ppm solutions in deionized
water.
Amine Cloud point ( TCl) [°C]
Ethylamine 64
n-Propylamine o20
Iso-propylamine 20
sec-Butylamine o20
Pyrrolidine 495
253
Table 6
Summary of average onset (To) and rapid hydrate formation (Ta) temperatures for
the n-propylamine derivative of PVDMA-I at different concentrations.
Concentration [ppm] To(av) [°C] Ta(av) [°C] To(av) – Ta(av) [°C]
1000a 12.3 11.9 0.4
2500 10.1 9.7 0.4
5000a 9.0 8.8 0.2
7000a 8.2 7.5 0.7
a
Average of three results.
Fig. 12. Onset (To) and rapid hydrate formation (Ta) temperatures for KHI tests at
different concentrations of the n-propylamine derivative of PVDMA-I.
was hard to specify. Decreasing the number of carbons on the
amine moiety to two, gives an expected increase in TCl to 64 °C. On
the other hand, the performance of this more soluble ethylamine
derivative was found to be poorer than the propylamine deriva-
tives. This may be due to only partial solubility of the propylamine
derivatives at hydrate forming temperatures. Work by Roth's
group on this polymer class shows that TCl decreases with in-
creasing polymer molecular weight (Zhu et al., 2013). In fact, a
polymer can go from being soluble in water with a cloud point of
7.9 °C to insoluble at all temperatures down to 0 °C at a higher
molecular weight.
As the n-butylamine derivative of PVDMA was insoluble in
water at all temperatures down to 0 °C, we prepared the sec-bu-
tylamine derivative instead. However, increasing the number of
pendant carbons from three (for the propylamine derivatives) to
four, did not seem to improve the performance. The 2500 ppm
solution of sec-butylamine derivative was observed to be quite
cloudy with signs of precipitation compared to the solutions of the
propylamine derivatives at room temperature. This indicates that
this sec-butylamine derivative is probably significantly less soluble
than 2500 ppm, which will naturally affect its KHI performance.
The pyrrolidine derivative of PVDMA-1 gave a similar KHI result as
the ethylamine derivative, which may reflect the high cloud point
of both polymers.
3.3. Performance testing of the n-propylamine derivative of PVDMA-I
at different concentrations
The PVDMA derivative that showed the best performance in
the KHI experiments at 2500 ppm was the n-propylamine deri-
vative of the VDMA polymer with the lowest molecular weight,
PVDMA-I. Hence, the performance of this polymer at a range of
concentrations (1000, 2500, 5000 and 7000 ppm) in deionized
water was investigated. The average of the To and Ta values from
three KHI test results are shown in Table 6 together with the ten
254 L.H.S. Ree et al. / Chemical Engineering Science 152 (2016) 248–254
results obtained at 2500 ppm. All data points are presented in
Fig. 12 to show the scattering of the data. As expected the per-
formance of the polymer improves as the concentration is in-
creased. Even at 1000 ppm the polymer performed well compared
to pure water.
4. Conclusion
A series of polymers of 2-vinyl-4,4-dimethylazlactone (VDMA)
of varying molecular weights modified with small organic amines
have been synthesized. Their performance as kinetic hydrate in-
hibitors (KHIs) has been investigated in high pressure steel rocking
cells using a Structure II-forming synthetic hydrocarbon gas mix-
ture. It was found that the PVDMA polymer with the lowest mo-
lecular weight (Mn ¼1845 g/mole by 1H NMR) performed the best.
It was also found that the n-propylamine derivative performed the
best of the amine derivatives. The cloud point of this polymer
derivative was found to be lower than ambient temperature,
which is considered too low for practical oilfield applications.
However, high cloud point PVDMA derivatives such as the ethy-
lamine or pyrrolidine derivatives still gave reasonable KHI per-
formance. The KHI performance of the n-propylamine derivative of
PVDMA-I was tested at different concentrations in the range 1000–
7000 ppm. It was found that the performance improved as the
polymer concentration was increased.
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