198 | Macromol. Symp. 2015, 353, 198–204 DOI: 10.1002/masy.

201550327

Copolymerization of Acrylamide with 9- and

10-Acrylamidodecanoic Acids
Desnelli,1,2 D. Mujahidin,3 Y. Permana,1 Chyntia L. Radiman*1

Summary: Copolymerization of acrylamide with 9- and 10-acrylamidodecanoic

acids (AADAs) has been carried out by free radical polymerization using ammonium
persulphate as an initiator. AADA monomer was synthesized from 9-decenoic acid
via Ritter reaction using acrylonitrile and sulfuric acid as catalyst. Characterization of
monomers and the resulting copolymers were performed by Nuclear Magnetic
Resonance (NMR) and Fourier Transform-Infrared (FT-IR) spectroscopy, respectively.
The intrinsic viscosities of copolymers with various compositions were measured
using Ubbelohde capillary viscometer in 1.0 M sodium chloride solution. It was found
that the intrinsic viscosity of the copolymers decreased with increasing the AADA
monomer content.

Keywords: acrylamide; copolymerization; 9- and 10- acrylamidodecanoic acids; 9-decenoic

acid; Ritter reaction

Introduction consequently, control the fluid mobility of

Petroleum oil, as one of the non-renewable
resources, can not compete with the steady
increasing demand of fuels. Its production
has started to decline due to difficulties to
take out all the oil in the wells, especially in
the old ones. It is roughly estimated that
50-60% of the original oil in place (OOIP)
still remains in the reservoir after primary
and secondary recoveries.[1,2] Therefore,
the problem of low productivity in the old
wells should be overcome by applying
enhanced oil recovery (EOR) methods.[3]
Polymer flooding is one of EOR methods in
which high molecular weight polymer is
injected.[4] This polymer has to be water
soluble, increase the viscosity of water and
1 Acrylamido-2-methylpropanesulfonate
Division of Inorganic and Physical Chemistry, Faculty
of Mathematics and Natural Sciences, InstitutTekno-
logi Bandung, JalanGanesha 10, Bandung 40132,
Indonesia
Fax: (þ62)-022-2504154;
E-mail: cynthia@mail.chem.itb.ac.id
2
Department of Chemistry, Universitas Sriwijaya,
Jalan Palembeng-Prabumulih, Km 32, Indralaya
30662, Indonesia
3
Division of Organic Chemistry, Faculty of Mathe-
matics and Natural Sciences, InstitutTeknologi Ban-
dung, JalanGanesha 10, Bandung 40132, Indonesia
water in the reservoir.[5] Polyacrylamide, a
polymer derived from fossil resources, is
commonly used for this application.[6]
However, it has some drawbacks such as
its instability at high temperatures and
its low resistance to high salinity.[7] In this
work, attemps have been done to explore
other resources as basic materials in order
to prepare polymers for EOR applications.
Based on our literature studies, the co-
polymerization of acrylamide N-phenyl-
maleimide (N-PMI) and acrylamide with
N-allylbenzamide (NABI) resulted in
copolymers having high temperature resist-
ance, salt tolerance and shear resistance.[8]
Sabhapondit et al had conducted a syn-
thesis of high molecular weight copolymer
of N,N-dimethyl acrylamide with Na-2-
(NNDAM-NaAMPS) which is stable up to
120
C for a period of one month.[9]
Indonesia is one of the largest exporter
of palm oil. This oil contains 30-45% of
oleic acid which can be reacted to produce a
monomer called methyl-9-decenoate. So, it
is expected that in the long run a new
polymer for EOR application can be
synthesized from natural resources. For

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Macromol. Symp. 2015, 353, 198–204
this reason, a preliminary study have been
done using a hydrolysis product of methyl-
9-decenoate, namely 9-decenoic acid.
A chemical reaction called Ritter reaction
is known as a method for preparing
amide compounds.[10] It is expected that
the presence of long-chain alkyl can
improve the solution properties of acryl-
amide derivatives in water. In this work, the
9-decenoic acid was reacted with acryla-
mide to produce 9- and 10-acrylamidode-
canoic acids (AADAs) using Ritter
reaction and the resulting AADAs were
then copolymerized with acrylamide (AM).
The effect of composition on the intrinsic
viscosity of copolymer solutions were
determined. 1H NMR and FTIR spectro-
scopy were also employed in the structural
characterization of the monomer and the
produced copolymers.
Experimental Part
Materials
9-Decenoic acid (90%), ammonium per-
sulphate and acrylonitrile (99%) were
obtained from Sigma, while acrylamide
(99%), sulphuric acid (98%), sodium
chloride and sodium hydroxide were
obtained from Merck. Acetone (technical
grade) was obtained from a local supplier
and nitrogen gas (80%) was from PT.
Aneka Gas. Deionized water was used in
the appropriate experiment. Acetone
was distilled before use and the other
chemicals were used without further
purification.
Synthesis of 9- and 10-Acylamidodecanoic
acids
The synthesis of 9- and 10-acrylamidode-
canoic acids (AADAs) were carried out
using a procedure described by Yang
et al.[11] First, 9-decenoic acid (0.1 mol)
and acrylonitrile (0.5 mol) were mixed and
stirred at 5
C in a two-necked round-
bottom flask. After that, 0.4 mol of H2SO4
was added dropwisely during 30 min. The
mixture was then stirred for 12 h at room
temperature under nitrogen atmosphere.
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| 199
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Furthermore, the mixture was poured into
75 mL of crushed ice and stirred for 30 min.
The mixture was then separated and
extracted twice with methylene chloride.
The methylene chloride layer was sepa-
rated from water, and then dried with
anhydrous Na2SO4. Finally, the mixture
was evaporated to produce a viscous
product.
Synthesis of Copolymer
Acrylamide (AM) and 9- and 10-acrylami-
dodecanoic acids (AADAs) were copoly-
merized using 0.1 mol% ammonium
persulphate as an initiator with various
AM: AADA ratio. The molar ratio AM:
AADA were 100: 0 (PAM), 98: 2
(AMAADA2), 95: 5(AMAADA5) and
80: 20 (AMAADA20). The copolymeriza-
tion was conducted in a 250 mL four-
necked round-bottom flask equipped with
a mechanical stirrer, a nitrogen inlet and
thermometer. A certain amount of AM
and AADA with designated ratio was
dissolved in 100 mL deionized water.
The pH of entire mixture was adjusted to
9.0 by dropwise addition of 0.5 M NaOH.
Then, 0.1 mol % ammonium persulphate
was added to the mixture. The flask was
placed in oil bath and the polymerization
was carried out at 50
C for 10 h under
nitrogen atmosphere. The reaction mixture
was poured into a flask containing an excess
amount of acetone. The precipitated poly-
mer was washed twice with acetone to
remove the homopolymer. The polymer
was finally dried in a vacuum oven for 48 h.
Spectroscopic Measurement
The chemical structures of monomer and
copolymer were determined by Perkin
Elmer FT-IR spectrophotometer using
KBr pellets. The 1H NMR spectra of
9- and 10-arylamidodecanoic acids were
taken in CDCl3, while the ones of copoly-
mers in D2O.
Intrinsic Viscosity Determination
The intrinsic viscosity of copolymer was
carried out by the viscometry method using
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200 | Macromol. Symp. 2015, 353, 198–204
O
+ H2SO4
C N
OH
9-Decenoic Acid Acrylonitrle
Figure 1.
Synthesis reaction scheme of 9- and 10-acrylamidodecanoic acids (AADAs).
1.0 sodium chloride solution at 25
C. The
intrinsic viscosity [h] was determined by
plotting the reduced specific viscosity (hsp/c)
of the solution against its corresponding
concentration and extrapolating it to zero
concentration.
Results and Discussion
Synthesis of Monomer 9- and
10-acrylamidodecanoic Acids (AADAs)
The AADA monomer was synthesized
based on the Ritter reaction in which an
amide is formed due to reaction of alkene
with nitrile in the presence of concentrated
Figure 2.
The 1H-NMR spectrum of AADA monomer.
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O O
N OH
H
H2O
9-Acrylamidodecanoic Acid
O
OH
N
H O
10-Acrylamidodecanoic Acid
sulfuric acid and hydrolysis.[12] The reac-
tion scheme is shown in Figure 1.
The reaction of acrylonitrile with
9-decenoic acid yielded a mixture of two
products of acrylamide derivatives, namely
9-acrylamidodecanoic acid and 10-acrylami-
dodecanoic acid (AADAs). The 1H-NMR
spectrum of AADA monomer in CDCl3 is
shown in Figure 2 and the chemical shifts and
the type of corresponding protons is listed in
Table 1.
The chemical shift value at 0.9 ppm and
3.8 ppm were assigned to the proton of -CH3
and -CH-, respectively. These chemical shift
values indicated the structure number (1) or
9-acrylamidodecanoic acid. Furthermore,
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Macromol. Symp. 2015, 353, 198–204 | 201

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Table 1. Table 2.
The chemical shift of 1H-NMR spectrum of AADA The characteristic absorption bonds of FTIR spectra
monomer. for 9-decenoic acid and AADA monomer.
Chemical shift [ppm] Type of proton Compound Band Type of Functional
[cm1] vibration Group
0.9 -CH3
3.8 -CH- 2500-3000 stretching O-H
3.5 -CH2NHCO- 9-decenoic 1710 stretching C¼O
5.6 -NHCOCH ¼ CH2 acid
6.1 -NHCOCH ¼ CH2 1642 stretching C¼C
6.2 -NHCOCH ¼ CH2 3422 stretching O-H
3282 stretching N-H
AADA 1550 bending N-H
monomer
the structure number (2) or 10-acrylamido- 3190 N-H (second-
decanoic acid were correlated to the chem- ary amide)
1703 stretching C ¼ O (acid)
ical shift value at 3.5 ppm. The peak at 1656 stretching C¼O
chemical shift 4.0 ppm is the chemical shift of (amide)
the proton due to difference in the geometry
structures of 9- and 10 acrylamidodecanoic
acids (AADAs). Based on 1H-NMR, signal copolymer (1) and copolymer (2) which
intensities of –CH- and –CH2-, a mixture of theirs structures are shown in Figure 4.
9- and 10-acrylamidodecanoic acids have These copolymers dissolved completely in
ratio of 1:1. water. They fulfilled one of the require-
The FT-IR spectrum of AADA mono- ments for enhanced oil recovery (EOR)
mer compared to its of 9-decenoic acid is applications.
shown in Figure 3. The characteristic The 1H-NMR spectra of AM-AADA
absorption bonds of AADA monomer copolymer with a % mol ratio of 80 to 20
and 9-decenoic acid are listed in Table 2. (designated as AMAADA20) is shown
Based on the FT-IR spectra of 9- and 10 in Figure 5. The characteristic chemical
acrylamidodecanoic acids (AADAs), it was shift value and the corresponding protons
concluded that the AADA monomer has are listed in Table 3. The chemical shift
succesfully formed. at 3.7 ppm and 0.8 ppm indicated the
copolymer with structure (1), while
Synthesis of Copolymers copolymer with structure (2) appeared
Copolymerization of acrylamide (AM) at 3.5 ppm. On the other hand, vinylic
and 9- and 10-acrylamidodecanoic acids protons at 5.6 ppm, 6.1 ppm and 6.2 ppm
(AADAs) produced a mixture of disappeared. This data indicated that the

Figure 3.
FTIR spectrum of (a) 9-decenoic acid and (b) AADA monomer.

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The copolymerization of acrylamide (AM) and 9- and 10-acrylamidodecanoic acids (AADAs) yielding structures (1)

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

H-NMR spectrum of AMAADA20 copolymer.
Macromol. Symp. 2015, 353, 198–204

Figure 4.

Figure 5.
and (2).

1
202 |
Macromol. Symp. 2015, 353, 198–204 | 203

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Table 3. Table 4.
Data of 1H-NMR spectrum of AMAADA20 Analysis of FTIR spectrum of copolymer and PAM.
copolymer.
Compound Band Type of Functional
Chemical shift [ppm] Type of proton [cm1] vibration Group
3.5 -CH2-NH-C ¼ O- 2400 stretching N-H
3.7 -CHNH- PAM 1658 stretching C¼O
0.8 -CH3 1620 bending N-H/NH2
3448 stretching N-H
1556 bending N-H
1672 stretching C ¼ O (amide)
copolymers were successfully formed Copolymer 1449 bending CH3
3190 bending secondary N-H
through this reaction. 1637 bending N-H/NH2
The FT-IR spectroscopic measurement 723 bending CH2
was also used to confirm the above
mentioned data. The FTIR spectrum of
AMAADA copolymer compared to poly-
acrylamide (PAM) is shown in Figure 6 and Table 5.
their characteristic absorption bonds are Intrinsic viscosity of polymer.
listed in Table 4. Sample code Feed composition [mol %] [h] [dL/g]
The peak at 723 cm1 shows the AM: AADA
absorption bands of methylene rocking
PAM 100 0 5.397
vibration indicating the presence of AMAADA2 98 2 2.947
straight-chain alkanes of seven or more AMAADA5 95 5 2.066
carbon atoms.[13] The peak at 3190 cm1 is AMAADA20 80 20 0.888
attributed to bending vibration of secon-
dary amide group (N-H) which distin-
guishes copolymer from PAM. The –CH3
absorption band appeared at 1449 cm1 Intrinsic Viscosity of Copolymers
indicates the existence of structure I. The Based on intrinsic viscosity analysis
carbonyl peaks in AADA monomer over- (Table 5), the higher percentage of
laped with carbonyl from AM while the AADA monomer, the lower of its intrinsic
C ¼ C absorption at 1620-1680 cm1, viscosity. It shows that the hydrophobic
3095-3075 cm1, 985-995cm1and 900-950 groups of AADA long alkyl chain
cm1 disappeared. These characteristics can undergo intramolecular association
peaks confirmed the successful copolymer- according to the results of other
ization of AM and AADA. researchers.[1]

Figure 6.
FT-IR spectrum of (a) PAM and (b) copolymer (AM/AADA).

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204 | Macromol. Symp. 2015, 353, 198–204
Conclusion
The AADA monomer and water soluble
AM-AADA copolymers have been suc-
cessfully synthesized in this work. The
higher content of AADA in AM-AADA
copolymer leads to the lower intrinsic
viscosity of its copolymers due to intra-
molecular association among the molecules.
Acknowledgments: We acknowledge DIKTI for
financial supporting this research, Republic of
Indonesia.
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