Article

pubs.acs.org/EF

N,N‑Dimethylhydrazidoacrylamides. Part 3: Improving

Kinetic Hydrate Inhibitor Performance Using Polymers
of N,N‑Dimethylhydrazidomethacrylamide
Lilian H. S. Ree,† Mohamed F. Mady,†,‡ and Malcolm A. Kelland*,†
†
Department of Mathematics and Natural Science, Faculty of Science and Technology, University of Stavanger,
N-4036 Stavanger, Norway
‡
Department of Green Chemistry, National Research Centre, 33 El Bohouth Street, Post Office 12622, Dokki, Giza, Egypt

ABSTRACT: A series of homopolymers of N,N-dimethylhydrazidomethacrylamide (DMHMAM) and copolymers with

(N-isopropylmethacrylamide) (IPMAM) have been synthesized and investigated as kinetic hydrate inhibitors (KHIs) with a
structure-II-forming synthetic hydrocarbon gas mixture in high-pressure steel rocking cells. The same polymerization method to
give similar low molecular weights was used to aid KHI performance comparison. The homopolymer polyDMHMAM was found
to give good KHI performance, significantly better than the related homopolymer, poly(N,N-dimethylhydrazidoacrylamide)
(polyDMHAM), which does not have methyl groups in the backbone. This is in agreement with previous studies on
N-alkylmethacrylamides. PolyDMHMAM also has no cloud point in deionized water up to 95+ °C, making it suitable for
injection in high-temperature wells. A 1:1 N,N-dimethylhydrazidomethacrylamide/N-isopropylmethacrylamide copolymer
(1:1 DMHMAM/IPMAM copolymer; Mn = 2100) also exhibited no cloud point in deionized water and showed an improved
KHI performance over polyDMHMAM homopolymer (Mn = 2300) and poly(N-isopropylmethacrylamide) (Mn = 1300) of
similar low molecular weights. Other ratios of monomers in DMHMAM/IPMAM copolymers did not show an improvement
on the performance compared to the other copolymers. Protonation of polyDMHMAM to give only quaternary
dimethylhydrazinium groups strongly lowers the KHI performance. High pH (8−9) also gave a worse performance than at
pH 6.5, suggesting that partial protonation of polyDMHMAM is optimal for the best KHI performance.

1. INTRODUCTION
Gas hydrates are ice-like clathrate solids formed by water and
small gas molecules, such as carbon dioxide, methane, ethane,
and/or propane, at lower temperatures and elevated pressures.1−3
These can potentially cause plugging of oil and gas flowlines,
causing lost production. In addition, removal of gas hydrate
plugs is a very costly operation.
Kinetic hydrate inhibitors (KHIs) are a class of low-dosage
hydrate inhibitors (LDHIs) that are currently being used in the
upstream oil and gas industry to prevent plugs of gas hydrates
from forming in the flowlines.4−6 KHIs are typically relatively
small, water-soluble polymers, optionally with added synergists.
They often function by delaying the gas hydrate nucleation
process, while some KHIs also delay crystal growth. For field
operations, the delay time to hydrate nucleation (induction
time) and its dependence upon the subcooling at the field
conditions are the most critical factors.
A whole range of water-soluble polymers has been studied as
potential KHIs, most of them having hydrophobic pendant
groups attached to strongly hydrogen-bonding amide or
imide groups to keep them in the water phase.4 N-Alkyl- and
N,N-dialkylacrylamide polymers and copolymers are one class
that have been widely investigated as KHIs. This includes both
methacryl- and acrylamide polymers.7−11 Polymers based on
N-isopropylmethacrylamide (IPMAM) have been commercialized
and are now used in various field operations (Figure 1). Studies
by ExxonMobil first showed that the extra backbone methyl
groups in IPMAM polymers improved the KHI performance
relative to N-isopropylacrylamide (IPAM) polymers.12,13
Figure 1. Structures of (left) N-isopropyl(meth)acrylamide (R = H
or CH3) and (right) N,N-dimethylhydrazido(meth)acrylamide (R = H
or CH3).
Despite good performance, there are some limitations to the
use of, for example, IPMAM and IPAM polymers as KHIs. One
of these limitations is the low cloud points (TCl), as well as
deposition points. Homopolymers of IPAM and IPMAM have
cloud/deposition points around 30−40 °C in deionized (DI)
water. Hence, in the field, you might experience problems of
precipitation at the injection point as a result of too high of a
temperature. One method of increasing the cloud/deposition
point of alkylacrylamide polymers is to copolymerize with a more
hydrophilic monomer. This often leads to less efficient KHIs.4
Work performed in our group has shown promising results by
copolymerizing hydrazide monomers with N-alkylacrylamides
and N-vinylcaprolactam (VCap).14,15 In these studies, a new
KHI monomer, N,N-dimethylhydrazidoacrylamide (DMHAM),
Received: September 14, 2015
Revised: November 10, 2015
Published: November 16, 2015

© 2015 American Chemical Society 7923 DOI: 10.1021/acs.energyfuels.5b02079

Energy Fuels 2015, 29, 7923−7930
Energy & Fuels Article

was used, which is closely related to IPAM by exchanging the

secondary carbon atom in the isopropyl group with a nitrogen
atom (Figure 1). The hydrazine-based starting material
used to make the side chains of the DMHAM polymers is
N,N-dimethylhydrazine, a cheap commercial chemical used in
rocket fuels.16,17 The homopolymer poly(N,N-dimethylhydra-
zidoacrylamide) (polyDMHAM) has no cloud point up to
100 °C in DI water but showed only mediocre KHI perfor-
mance. Copolymers with IPAM or VCap gave improved
performance. However, we were interested in improving the
performance further. On the basis of the work by ExxonMobil
showing that adding an extra methyl group to the backbone
could improve KHI performance,12,13 we sought to synthesize
polymers using N,N-dimethylhydrazidomethacrylamide
(DMHMAM). DMHMAM has an extra methyl group in
the backbone compared to DMHAM. However, early attempts
to synthesize polymers of DMHMAM in the same way as poly- Figure 2. Synthesis of homo- and copolymers of DMHMAM and
mers of DMHAM were unsuccessful. IPMAM.
In this study, we report the successful high yield synthesis of
DMHMAM homo- and copolymers and their KHI perfor- The polymer solution was cooled to room temperature, and solvents
mance using a structure-II-forming synthetic gas mixture at were removed in vacuo to leave a pale yellowish solid. Using this
varying pH. general procedure, a series of polyDMHMAM homopolymers with
different molecular weights were synthesized using different initiator
2. EXPERIMENTAL SECTION ratios of AIBN. The molecular weights of the new polymers were
determined by GPC, as tabulated in Table 1.
2.1. Chemicals. All chemicals were purchased from VWR and
Sigma-Aldrich. All solvents were used as purchased without further Table 1. Molecular Weight of Novel Polymers According
purification. Caution: N,N-Dimethylhydrazine is toxic and carcino-
genic and can be adsorbed through the skin. Care must be taken, and to GPCa
adequate gloves must be worn, when using this chemical. initiator number-average
2.2. Characterization of Polymeric KHIs. Nuclear magnetic (AIBN) molecular weight polydispersity
resonance (NMR) spectra of the polymers were recorded on a polymer (molar ratio) (%, w/w) (Mn) (g/mol) index (PDI)
300 MHz Varian NMR spectrometer to monitor the conversion of the polyDMHMAM-I (100%) 2 3000 2.20
monomers. The polymer samples were dissolved in D2O at room polyDMHMAM-II (100%) 4 2300 1.79
temperature. polyDMHMAM-III (100%) 10 5000 1.76
The molecular weight and molecular weight distribution of the new
polyIPMAM (100%) 2 1300 1.93
polymers were determined by gel permeation chromatography (GPC),
using polyethylene glycol samples as molecular-weight standards in DMHMAM/IPMAM (2:1) 2 16300 2.05
0.2 M NaCl. GPC was performed with a HLC 8220 chromatograph DMHMAM/IPMAM-I (1:1) 2 6700 3.36
(Tosoh Co., Tokyo, Japan) equipped with TSK gel super HM-H DMHMAM/IPMAM-II (1:1)b 2 2100 3.80
H4000/H3000/H2000 (7.8 mm diameter, 150 mm × 3), Tosoh Co. DMHMAM/IPMAM (1:2) 2 4700 3.47
2.3. Cloud Point (TCl) Measurement. A 2500 ppm solution of DMHMAM/IPMAM (1:4) 2 11000 2.03
polymer in DI water was carefully heated at about 2 °C/min, making DMHMAM/IPMAM (1:9) 2 5500 2.93
visual observations throughout. The cloud point (TCl) was determined a
Molar ratios in copolymers are given in parentheses. b
Polymer
as the temperature at which the first sign of haze in the solution was synthesis method using heating at 80 °C only, for 16 h.
observed. Because the products of the polymerization reactions of
DMHMAM were isolated as the HCl salt of the polymer in interest,
the polymer solution was neutralized using sodium bicarbonate prior 2.5.1.1. PolyDMHMAM-I (2% AIBN). Yield: 88%. 1H NMR (D2O,
to measuring the cloud point. In this way, the cloud point of the non- 300 MHz) δ: 1.02−1.14 (br, 3H, CH3), 1.60−1.92 [br, 2H, −CH2−
ionic form of the polymer was measured. C(−CO)H−], 2.89−3.01 [br, 6H, −N(CH3)2].
2.4. Synthesis of DMHMAM. DMHMAM monomer was 2.5.1.2. PolyDMHMAM-II (4% AIBN). Yield: 90%. 1H NMR (D2O,
synthesized from methacryloyl chloride and N,N-dimethylhydrazine 300 MHz) δ: 1.04−1.19 (br, 3H, CH3), 1.65−1.98 [br, 2H, −CH2−
in the presence of triethylamine in diethyl ether as described in our C(−CO)H−], 2.69−3.02 [br, 6H, −N(CH3)2].
previous work.14 2.5.1.3. PolyDMHMAM-III (10% AIBN). Yield: 85%. 1H NMR (D2O,
2.5. Synthesis of Novel Polymers. 2.5.1. N,N-Dimethylhydra- 300 MHz) δ: 1.02−1.14 (br, 3H, CH3), 1.60−1.92 [br, 2H, −CH2−
zidomethacrylamide Hydrochloride (polyDMHMAM·HCl) Homopol- C(−CO)H−], 2.89−3.01 [br, 6H, −N(CH3)2].
ymer (Figure 2). In a Schlenk tube equipped with Young’s tap and a 2.5.2. N-Isopropylmethacrylamide (polyIPMAM) Homopolymer
magnetic stir bar were placed N,N-dimethylhydrazidomethacrylamide (Figure 2). To a 100 mL round-bottom flask equipped with a magnetic
(0.5 g, 4.91 mmol) and 2% (w/w) azobis(isobutyronitrile) (AIBN) in stirring bar was added N-isopropylmethacrylamide (1.0 g, 7.87 mmol)
aqueous isopropyl alcohol (5.0 mL) and hydrochloric acid (1.0 equiv). and aqueous isopropyl alcohol (10 mL). AIBN (2%, w/w) was added,
The tube was flushed with oxygen-free nitrogen for at least 10 min and and nitrogen was bubbled through the mixture for 10 min. The mix-
kept under the protection of a nitrogen atmosphere. The reaction ture was then heated to 60 °C with stirring for 12 h. After completion
mixture was allowed to heat stepwise from room temperature to 40, of the reaction (monitored by 1H NMR), the solution was allowed to
60, and up to 80 °C, at which time an additional 2% (w/w) AIBN was cool to room temperature. Solvents were removed in vacuo to leave a
added. The reaction mixture was kept at each temperature overnight. white solid as a high yield of polyIPMAM product.
The reaction was monitored by 1H NMR spectroscopy to determine 2.5.2.1. PolyIPMAM (2% AIBN). Yield: 85%. 1H NMR (D2O,
the percentage conversion of the monomer. After this time, the 300 MHz) δ: 0.94−1.28 (br, 6H, CH3), 1.70−1.75 [br, 2H, −CH2−
reaction medium became viscous and the stirring was stopped. C(−CO)H−], 3.85−3.89 [br, 1H, −CH−(CH3)2].

7924 DOI: 10.1021/acs.energyfuels.5b02079

Energy Fuels 2015, 29, 7923−7930
Energy & Fuels Article

2.5.3. Synthesis of Copolymers of DMHMAM and IPMAM (Figure 2). the total volume of water and hydrochloric acid was 1 mL. The
The example shown here is for a 1:1 molar ratio copolymer. To a solution was flushed with nitrogen several times using a standard
Schlenk tube equipped with a glass cap and a magnetic stirring pump-fill technique. Under the protection of nitrogen, the reaction
bar were added DMHMAM (0.500 g, 3.90 mmol), IPMAM (0.496 g, mixture was heated from room temperature to 40 °C and was stirred
3.90 mmol), AIBN [20 mg, 2% (w/w) of monomer total], isopropyl at this temperature for about 16−18 h. Then, an additional AIBN
alcohol (3.0 mL), and diluted hydrochloric acid (2.0 M, 1.95 mL, [20 mg, 2% (w/w) of monomer total] was added; the temperature was
3.90 mmol, 1.0 equiv relative to DMHMAM). If the required volume increased to 60 °C; and the mixture was stirred at this temperature
of diluted hydrochloric acid was less than 1 mL, water was added until for an additional 16−18 h. This step was repeated once more, and
the temperature was then increased to 80 °C. After 16−18 h at this
temperature, the reaction mixture became viscous. The polymer
solution was cooled to room temperature, and the product was
precipitated by a mixture of acetone/n-hexane (1:1). The solvent was
decanted off, and the polymer was dried under vacuum to leave a light
orange solid. The reaction was monitored by 1H NMR spectroscopy
to determine the percentage of conversion of the monomer. It was
found that, using this method, the monomer conversion was at least
95% according to NMR. Hence, it can be assumed that the ratios of
DMHMAM/IPMAM for the different copolymers are roughly the
same as the ratios of monomers added. Five DMHMAM/IPMAM
copolymers with different molecular weights were synthesized by the
above procedure. The yields after workup ranged from 53 to 99%.
The molecular weights of the new polymers are summarized in Table 1.
We attempted as best as possible to obtain similar polymer molecular
weights using the same polymerization method for ease of KHI
performance comparison.
2.6. High-Pressure Gas Hydrate Rocker Rig Equipment Test
Methods. Kinetic hydrate inhibition tests were conducted in five
high-pressure 40 mL steel rocking cells each containing a steel ball as
previously described by our research group.18 The equipment was
Figure 3. Rocker rig with the five steel rocking cells positioned in the manufactured and supplied by PSL Systemtechnik, Germany (Figure 3).
cooling bath. The gas composition used was a standard synthetic natural gas mixture
(SNG), as given in Table 2, which preferentially forms structure II gas
Table 2. Composition of SNG hydrates.
At the start of each “constant cooling” experiment, the pressure was
component mol % approximately 76 bar. The equilibrium temperature (Teq) at this
methane 80.67 pressure has been determined by standard laboratory dissociation
experiments, warming at 0.025 °C/h for the last 3−4 °C.19,20 Five
ethane 10.20
repeated equilibrium tests were carried out, which gave Teq = 20.2 ±
propane 4.90
0.5 °C. This value is in good agreement with the calculated Teq value
isobutane 1.53 of 20.5 °C using PVTSim software of Calsep.
n-butane 0.76 The same “constant cooling” test procedure as previously described
N2 0.10 by our research group was used to evaluate the performance of the
CO2 1.84 novel KHI polymers.18 The test procedure was as follows: (1) Each

Figure 4. Example of pressure and temperature data versus time for five cells in a standard constant cooling KHI experiment of 2500 ppm
DMHMAM/IPMAM-I (1:1) copolymer.

7925 DOI: 10.1021/acs.energyfuels.5b02079

Energy Fuels 2015, 29, 7923−7930
Energy & Fuels Article

Figure 5. Example of how To and Ta was determined after a standard constant cooling test using 2500 ppm DMHMAM/IPMAM-I (1:1) copolymer.

cell was filled with 20 mL of DI water, in which the various polymers Table 3. Cloud Points (TCl) and Molecular Weights (Mn) of
had been dissolved to the desired concentration. (2) Air in the cells the Novel N,N-Dimethylhydrazidomethacrylamide Polymers
was removed by a combination of vacuum pumping and filling with
SNG to 3−5 bar and then a repeated step of vacuum pumping. polymer (molar ratio) Mn (g/mol) cloud point, TCl (°C)
(3) The cells were pressurized to 76 bar and rocked at 20 rocks per polyDMHMAM-I (100%) 3000 >95
minute at an angle of 40°. (4) The cells were cooled from 20.5 to polyDMHMAM-II (100%) 2300 >95
2.0 °C at a rate of 1.0 °C/h. (5) The pressure and temperature for polyDMHMAM-III (100%) 5000 >95
each individual cell as well as the temperature of the cooling bath were polyIPMAM (100%) 1300 39
logged on a computer. DMHMAM/IPMAM (2:1) 16300 >95
One example of a run with five cells under standard constant
DMHMAM/IPMAM-I (1:1) 6700 >95
cooling conditions is presented in Figure 4. The data are collected for
DMHMAM/IPMAM-II (1:1)a 2100 >95
the 1:1 copolymer of DMHMAM and IPMAM at a concentration of
2500 ppm. Because each cell is a closed system during the experiment, DMHMAM/IPMAM (1:2) 4700 81
a linear pressure decrease is seen as a result of the temperature being DMHMAM/IPMAM (1:4) 11000 71
reduced. The first deviation from this linear pressure decrease is DMHMAM/IPMAM (1:9) 5500 40
defined as the observed onset temperature for hydrate formation, To, a
Polymer synthesis method using heating at 80 °C only, for 16 h.
even though nucleation may have occurred earlier on an undetectable
scale. At some time after this initial hydrate formation temperature, a
rapid pressure decrease is seen, indicating rapid hydrate growth. The results show that the higher the amount of DMHMAM,
The temperature, Ta, at which the hydrate growth is at its most rapid is the higher the cloud point of the DMHMAM/IPMAM copoly-
determined at the steepest part. An example of the determination mers. For example, the 1:9 DMHMAM/IPMAM copolymer
of To and Ta is shown in Figure 5. The overall results show that the has a cloud point close to the polyIPMAM homopolymer,
temperatures are homogeneous for all cells in the water bath, and none whereas increasing the molar percentage of DMHMAM from
of the cells contain any systematic errors that lead to consistently 10 to 20% for the 1:4 copolymer raises the cloud point
better or worse results. substantially to 71 °C.
3.2. High-Pressure KHI Experiments at Neutral pH.
3. RESULTS AND DISCUSSION High-pressure natural gas hydrate constant cooling rocking cell
experiments were carried out using 2500 ppm of KHI in DI
3.1. Study of the Cloud Point of the New KHI water. Because the homo- and copolymers containing DMHMAM
Polymers. We have previously shown that DMHAM homo- were synthesized as HCl salts, the solutions were neutralized to
polymers exhibit no cloud point in DI water up to 100 °C.14 pH 7 with sodium bicarbonate prior to the performance testing
In addition, copolymerization of DMHAM with either IPAM or in the rocker rig. The tests were run with a pressure of
VCap has given copolymers with high cloud points and good approximately 76 bar, and the solutions were cooled from 20.5
KHI performance.14,15 It is also known that the addition of a to 2.0 °C at a cooling rate of 1.0 °C/h. Table 4 and Figure 6
methyl group to the backbone of a polyvinyl-based polymer will summarize the average onset temperatures (To) and fast
often enhance the KHI performance.12,13 Thus, polyIPMAM hydrate formation temperatures (Ta) from 8 to 12 parallel
shows better KHI performance than polyIPAM, although the experiments. Experiments with no additive are also included in
cloud point (TCl) of polyIPMAM is low, typically around the table as well as earlier results with polyDMHAM for
30−40 °C. In this continuation of our study of the cloud points comparison.14 The To value is considered the most important
of DMHAM polymers, we have investigated the cloud points of of the two temperature parameters because this refers to the
the newly synthesized DMHMAM/IPMAM polymers in DI first detection of hydrate formation, after which crystal growth
water. The results are summarized in Table 3. can potentially lead to hydrate plugging. The difference between
7926 DOI: 10.1021/acs.energyfuels.5b02079
Energy Fuels 2015, 29, 7923−7930
Energy & Fuels Article

Table 4. Constant Cooling KHI Tests of Neutral Polymer interesting observation because polyIPMAM has an undesirably
Solutions at 2500 ppm in the Multi-cell Rocker Rig low cloud point, which could cause problems upon injection
into hot well streams. PolyDMHMAM can overcome this
To(av) Ta(av) To(av) − Ta(av)
polymer (molar ratio) (°C) (°C) (°C) problem with its lack of cloud point in DI water while
maintaining good KHI performance.
no polymer 17.8 16.1 1.7
A third conclusion from the KHI test results is that
polyDMHAM-II (100%)14 13.5 10.7 2.8
DMHMAM/IPMAM (1:1) copolymer also exhibits no cloud
polyDMHMAM-I (100%) 9.0 8.2 0.8
point in DI water up to at least 95 °C but does show an
polyDMHMAM-II (100%) 8.9 7.8 1.1
improvement in the KHI performance compared to the
polyDMHMAM-III (100%) 10.1 8.8 1.3
polyIPMAM (100%) 9.5 8.5 1.0
homopolymer at similar molecular weights (Figure 6). Thus,
DMHMAM/IPMAM-I (1:1) 9.3 8.3 1.0
polyDMHMAM-II (Mn = 2300 g/mol) gave an average To
DMHMAM/IPMAM-II (1:1)a 8.2 7.3 0.9
value of 9.0 °C, whereas DMHMAM/IPMAM-II (1:1)
DMHMAM/IPMAM (1:2) 10.6 9.1 1.4
copolymer (Mn = 2100 g/mol) gave an average To value of
DMHMAM/IPMAM (1:4) 10.6 9.7 1.0
8.2 °C. A statistical t test gave a p value of 2.1 × 10−5, which is
DMHMAM/IPMAM (1:9) 10.6 9.2 1.5
less than 0.5, confirming the significance of this KHI
DMHMAM/IPMAM (2:1) 11.2 9.5 1.7
performance result to the 95% assurance level.21 Other ratios
of monomers in DMHMAM/IPMAM copolymers did not
a
Polymer synthesis method using heating at 80 °C only, for 16 h. show an improvement on the performance compared to the
other copolymers. This has been observed previously for
the To and Ta values gives some indication of the ability of N-vinyl caprolactam/N-methyl-N-vinyl acetamide copolymers.22
the additive to retard the gas hydrate crystal growth process, However, it should be pointed out that DMHMAM/IPMAM-II
although the onset temperature has to be considered when com- (1:1) copolymer was made using a slightly different procedure, in
paring hydrate growth rates. which polymerization was attempted before acidifying the
Some of the conclusions that we can draw from this study are solution and then reattempted with the addition of more AIBN
as follows. PolyDMHMAM (To = 8.9−9.0 °C at Mn = 2300− after acidification. If the standard polymerization method was
5000 g/mol) performs significantly better as a KHI than used, in which acidification was carried out first, we obtained
polyDMHAM (To = 12.8−13.5 °C at Mn = 900−1600 g/mol) DMHMAM/IPMAM-I (1:1) copolymer with a significantly
(Figures 6−8). The results are in accordance with the theory higher molecular weight (Mn = 6700 g/mol). This polymer
that adding a methyl group to alternate carbons in the polyvinyl gave a To value (9.3 °C) between those of the hompolymers
backbone does increase KHI performance13 (the reason for this polyDMHMAM (To = 8.9−9.0 °C) and polyIPMAM (To =
is thought to be due to the steric effect of the methyl groups 9.5 °C). This highlights the effect of the molecular weight and
opening out the polymer, giving a higher surface/polymer ratio polymerization method on the performance of KHI polymers,
and, therefore, better hydrate nucleation inhibition). It is also confirming once again the improved performance at very low
plausible that polyDMHMAM with an even lower molecular Mn values.4,5
weight than 2300 g/mol would have shown an even better 3.3. High-Pressure KHI Experiments of Homopoly-
performance because it is well-known that KHIs perform mers at Different pH. In our previous studies with
better at very low molecular weights (for a polymer, ca. 1500− DMHAM/VCap copolymers, we showed that pH has a signifi-
3000 g/mol) for monomodal distributions.4,5 Second, poly- cant effect on the KHI performance because the peripheral
DMHMAM performs on par with polyIPMAM. This is a very nitrogen atom of the hydrazide group can be protonated to

Figure 6. Average To (onset temperature) and Ta (temperature for fast hydrate formation) values from 8 to 12 experiments from constant cooling
KHI experiments with polymers at 2500 ppm and neutral pH.

7927 DOI: 10.1021/acs.energyfuels.5b02079

Energy Fuels 2015, 29, 7923−7930
Energy & Fuels Article

Figure 7. To and Ta values from the standard cooling KHI experiments of DMHMAM and IPMAM homopolymers at neutral pH.

Figure 8. To and Ta values from the standard cooling KHI experiments of DMHMAM and IPMAM copolymers at neutral pH.

hydrazidinium, changing the polymer from non-ionic to cationic.15

Thus, when aqueous solutions of the non-ionic polymers are
pressurized with the SNG, acidic gas CO2 will cause some
carbonic acid to form in the liquid water phase, lowering
the pH and quaternizing the hydrazido groups (Figure 9).
We continued these studies by investigating the effect of pH on
the performance of DMHMAM polymers.
To the best of our knowledge, pKa values for (meth)-
acrylamidodimethylhydrazide polymers have not been reported
previously. However, we can gain a fairly good idea of their
values based on known pKa values for related polyamines and
dialkylhydrazines. For example, a pKa of 7.21 has been reported
for 1,1-dimethylhydrazine.23 Further, poly(2-(dimethylamino)-
ethyl methacrylate) (PDMAEMA) has been reported to have a
similar pKa of 7.0.24 This polymer has pendant dimethylamino
groups, which are also present in polyDMHMAM. In contrast,
polyvinylamine with no alkyl groups on the nitrogen atom has a
pKa of 8.49, and similarly, poly-L-lysine, which also has primary
pendant amine groups, has a pKa of around 10.25,26 These last
two polymers are essentially protonated (i.e., quaternized) at
around pH 7. The above values for related polymers suggests
7928
Figure 9. Protonation of the hydrazido group to hydrazidinium in
DMHMAM polymers.
that unquaternized polyDMHMAM probably has a pKa value of
about 7.0−7.5. Thus, at 5000 ppm polymer concentration,
acidification to a pH value of 5 will give an almost fully
protonated polymer with pendant cationic dimethylhydrazi-
nium groups.
The results of KHI rocking cell tests with polyDMHMAM at
varying pH are given in Table 5 and Figure 10. First, we tested
with no added KHI using DI water and water with an added
base (NaOH) to raise the initial pH to 11.8. From statistical
t tests, it was found that the average To value did not drop
DOI: 10.1021/acs.energyfuels.5b02079
Energy Fuels 2015, 29, 7923−7930
Energy & Fuels Article

Table 5. Average To and Ta Values for polyIPMAM and polyDMHMAM-I at Different pH Values
polymer base pH prior to KHI testing pH after KHI testing To(av) (°C) Ta(av) (°C) To(av) − Ta(av) (°C)
no polymer 6.0 4.7 17.8 16.1 1.7
no polymer NaOH 11.8 6.8 17.5 16.0 1.5
polyIPMAM 5.6 4.8 9.5 8.5 1.0
polyIPMAMa NaOH 12.8 8.2 9.3 8.5 0.8
polyDMHMAM-Ia 2.3 2.2 15.0 13.5 1.5
polyDMHMAM-I NaHCO3 7.4 6.5 9.0 8.2 0.8
polyDMHMAM-Ia Na2CO3 10.8 8.1 9.8 7.9 1.9
polyDMHMAM-Ia NaOH 12.7 8.9 11.0 10.1 0.9
a
Four experiments only.

Figure 10. To and Ta as a function of pH for polyDMHMAM-I.

significantly (from 17.8 to 17.5 °C) using the higher pH
solution. The amount of base added was sufficient to drop the
pH after opening the cell to 6.8. The pH under the test
pressure would be expected to be somewhat lower as a result of
the higher partial pressure of CO2, which is not completely
quenched by the base. Next, we tested polyIPMAM. This
polymer contains amide groups, and the nitrogen atom will not
easily be protonated by solutions of carbonic acid compared to
the hydrazido DMHMAM polymers, and therefore, we expect
little effect on varying the pH. In accordance with this theory,
tests using a solution of polyIPMAM with an initially high pH
of 12.8 gave a similar average To value (9.3 °C) to tests with an
initially neutral solution of polyIPMAM (To = 9.5 °C). The pH
of both the neutral and based-treated solutions of polyIPMAM
were measured after the KHI tests after depressurization
and were found to be 4.8 and 8.2, respectively. Again, under
pressure, the pH would be expected to have dropped even
further for the initially neutral polymer solution.
Next, we tested polyDMHMAM-I homopolymer at varying
pH. At least four identical experiments were carried out for
each set of conditions. In this study, DMHMAM polymers were
first synthesized as the hydrochloride (HCl) salts and then
neutralized with 1 mol equiv of NaHCO3 prior to being tested
for KHI performance in the rocking cells. An initial pH value
before a test of 7.4 gave a pH after testing and depressurization
of about 6.5. This pH range causes partial protonation of the
dimethylhydrazido pendant groups based on an assumed pKa
value of 7−7.5. The hydrochloric salt of the polymer (no base
added) was also tested. The pH before and after the test was
7929
2.3 and 2.2, indicating complete protonation. This solution
showed poorer KHI performance (To = 15.0 °C) than the
neutral polymer. Increasing the pH to 10.8 and 12.7 prior to
KHI testing (and giving pH 8.9 after testing and little
protonation of the pendant groups) also gave poorer
performance than the neutral polymer, however, not as poor
as the acidic polymer, as seen from Table 5 and Figure 10.
We conclude that the protonated polymer form, containing
dimethylhydrazinium groups, as shown on the right in Figure 9,
is a much poorer KHI than the neutral polymer with
dimethylhydrazido groups. However, it appears that partial
protonation of polyDMHMAM is preferable for the best KHI
performance because, as the pH increases from 6.5 to 8.9, the
average To value increases from 9.0 to 11.0 °C.
The reason for the improved performance for the partially
protonated polymer is unclear. One speculative explanation is
that some cationic groups will raise the hydrophilicity of the
polymer, enabling the polymer to be essentially uncoiled in
solution and have less polymer−polymer interactions. This could
give a greater surface/volume ratio for the polymer, which will
increase the kinetic nucleation inhibition of gas hydrates by
perturbing the bulk water structure.4,5 At very low pH, the
polymer has all of the side groups quaternized, which means
none of these groups is hydrophobic in nature and capable of the
same degree of perturbation of the bulk water structure.
4. CONCLUSION
A series of homopolymers of DMHMAM and copolymers with
IPMAM have been synthesized and investigated as KHIs with a
DOI: 10.1021/acs.energyfuels.5b02079
Energy Fuels 2015, 29, 7923−7930
Energy & Fuels Article

structure-II-forming synthetic hydrocarbon gas mixture in high-
pressure steel rocking cells. The same polymerization method
to give similar low molecular weights was used to aid the KHI
performance comparison. The homopolymer polyDMHMAM
was found to give good KHI performance, significantly better
than the related homopolymer, polyDMHAM, which does not
have methyl groups in the backbone. This is in agreement with
previous studies on N-alkylmethacrylamides. PolyDMHMAM
also has no cloud point in DI water up to 95+ °C, making
it suitable for injection in high-temperature wells. A 1:1
N,N-dimethylhydrazidomethacrylamide/N-isopropylmethacry-
lamide copolymer (1:1 DMHMAM/IPMAM copolymer) also
exhibited no cloud point in DI water and showed an improved
KHI performance over polyDMHMAM homopolymer and
poly(N-isopropylmethacrylamide) when of similar low mole-
cular weight. Other ratios of monomers in DMHMAM/IPMAM
copolymers did not show an improvement on the performance
compared to the other copolymers. Protonation of poly-
DMHMAM to give quaternary dimethylhydrazinium groups
strongly lowers the KHI performance. High pH (8−9) also gave
a worse performance than at pH 6.5, suggesting that partial
protonation of polyDMHMAM is optimal for the best KHI
performance.
(14) Mady, M. F.; Kelland, M. A. Energy Fuels 2014, 28 (9), 5714−
5720.
(15) Mady, M. F.; Kelland, M. A. Energy Fuels 2015, 29 (2), 678−
685.
(16) Committee on Gulf War and Health; Literature Review of
Selected Environmental Particulates, Pollutants, and Synthetic
Chemical Compounds; Board on Health Promotion and Disease
Prevention; Institute of Medicine. Gulf War and Health; The National
Academies Press: Washington, D.C., 2005; Vol. 3. Fuels, Combustion
Products, and Propellants, pp 516, DOI: 10.17226/11180.
(17) Clark, J. D. Ignition! An Informal History of Liquid Rocket
Propellants; Rutgers University Press: New Brunswick, NJ, 1972; pp
45, ISBN: 0-8135-0725-1.
(18) Chua, P. C.; Kelland, M. A. Energy Fuels 2012, 26 (2), 1160−
1168.
(19) Gjertsen, L. H.; Fadnes, F. H. Ann. N. Y. Acad. Sci. 2000, 912,
722−734.
(20) Tohidi, B.; Burgass, R. W.; Danesh, A.; Østergaard, K. K.; Todd,
A. C. Ann. N. Y. Acad. Sci. 2000, 912, 924−931.
(21) Myers, R. H.; Myers, S. L.; Walpole, R. E.; Ye, K. Probablility
and Statistics for Engineers and Scientists; Pearson Education Interna-
tional: Upper Saddle River, NJ, 2007.
(22) Colle, K. S.; Oelfke, R. H.; Kelland, M. A. U.S. Patent 5,874,660
A, Feb 23, 1999.
(23) Hinman, R. L. J. Org. Chem. 1958, 23, 1587−1588.

■
(24) Bütün, V.; Armes, S. P.; Billingham, N. C. Polymer 2001, 42,
AUTHOR INFORMATION 5993.
(25) Shi, L.; Berkland, C. Macromolecules 2007, 40, 4635−4643.
Corresponding Author (26) Volodkin, D.; Ball, V.; Schaaf, P.; Voegel, J.-C.; Mohwald, H.
*E-mail: malcolm.kelland@uis.no. Biochim. Biophys. Acta, Biomembr. 2007, 1768 (2), 280−290.
Notes
Disclaimer: A patent application was submitted prior to
submission of this manuscript. This may give some relevant
financial interest in the future.
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
The authors thank Professor Hiroharu Ajiro at the Nara
Institute of Science and Technology for carrying out GPC
analysis.

■ REFERENCES
(1) Sloan, E. D., Jr.; Koh, C. A. Clathrate Hydrates of Natural Gases,
3rd ed.; CRC Press (Taylor & Francis Group): Boca Raton, FL, 2008.
(2) Makogon, Y. F. Hydrates of Hydrocarbons; PennWell Publishing
Company: Tulsa, OK, 1997.
(3) Carroll, J. Natural Gas HydratesA Guide for Engineers; Gulf
Professional Publishing (Elsevier Science): Boston, MA, 2003.
(4) Kelland, M. A. Advances in Materials Science Research; Wytherst,
M. C., Ed.; Nova Science Publishers, Inc.: Hauppauge, NY, 2011; Vol.
8.
(5) Kelland, M. A. Energy Fuels 2006, 20, 825.
(6) Perrin, A.; Musa, O. M.; Steed, J. W. Chem. Soc. Rev. 2013, 42 (5),
1996−2015.
(7) Colle, K. S.; Costello, C. A.; Talley, L. D.; Longo, J. M.; Oelfke,
R. H.; Berluche, E. WO Patent Application 96/08672, 1996.
(8) Kelland, M. A.; Rodger, P. M.; Namba, T. WO Patent Application
98/53007, 1998.
(9) Chua, P. C.; Kelland, M. A.; Ishitake, K.; Satoh, K.; Kamigaito,
M.; Okamoto, Y. Energy Fuels 2012, 26, 3577−3585.
(10) Chua, P. C.; Kelland, M. A.; Hirano, T.; Yamamoto, H. Energy
Fuels 2012, 26, 4961−4967.
(11) Mady, M. F.; Min Bak, J.; Lee, H.; Kelland, M. A. Chem. Eng. Sci.
2014, 119, 230−235.
(12) Colle, K. S.; Costello, C. A.; Talley, L. D.; Oelfke, R. H.;
Berluche, E. WO Patent Application 96/41786, 1996.
(13) Talley, L. D.; Oelfke, R. H. WO Patent Application 97/07320,
1997.

7930 DOI: 10.1021/acs.energyfuels.5b02079

Energy Fuels 2015, 29, 7923−7930