Deproteinized Natural Rubber Grafted with Polyacrylonitrile (PAN)/Polystirene (PS) and Degradation of its Mechanical Properties by Dimethyl Ether
Corresponding email: ty_indahsari@yahoo.co.id
Published at : 29 Jan 2020
Volume : IJtech
Vol 11, No 1 (2020)
DOI : https://doi.org/10.14716/ijtech.v11i1.1942
Indah Sari, T., Handaya Saputra, A., Bismo, S., R. Maspanger, D., 2020. Deproteinized Natural Rubber Grafted with Polyacrylonitrile (PAN)/Polystirene (PS) and Degradation of its Mechanical Properties by Dimethyl Ether. International Journal of Technology. Volume 11(1), pp. 15-25
| Tuti Indah Sari | Department of Chemical Engineering, Faculty of Engineering, Sriwijaya University, Kampus Indralaya, Indralaya 30662, Indonesia |
| Asep Handaya Saputra | Department of Chemical Engineering, Faculty of Engineering, Universitas Indonesia, Kampus UI Depok, Depok 16424, Indonesia |
| Setijo Bismo | Department of Chemical Engineering, Faculty of Engineering, Universitas Indonesia, Kampus UI Depok, Depok 16424, Indonesia |
| Dadi R. Maspanger | Indonesian Rubber Research Institute, Jl. Salak Bogor 16151, Indonesia |
Dimethyl ether (DME) is a clean fuel that has
moderate polarity, swells easily, and dissolves organic compounds. It has the
ability to attack some sealing materials and plastic components because of its
low viscosity. The modification of deproteinized natural rubber with
acrylonitrile (AN) monomer and styrene (ST) monomer by an emulsion
copolymerization process can be used to
obtain DPNR-g-PAN/PS copolymers. This process uses a stirred reactor with T =
65oC, P = 1 atm, initiator potassium persulfate (K2S2O8),
and an emulsifier sodium dodecyl sulfate (SDS). The copolymer DPNR-g-PAN/PS can
be used to seal storage for DME because it is
expected to reduce the degradation of rubber due to the presence of DME. The
parameters that were used in testing for the resistance of DPNR included
swelling, shrinking, the infrared spectrum obtained
through Fourier transform infra-red spectroscopy (FTIR), and changes in the
mechanical properties of DPNR after immersion. The
results of this research revealed that the presence of AN and ST can improve the
mechanical properties of DPNR. They also showed that an
increase in the concentration of AN decreased the swelling and increased the
shrinking of rubber. However, an increase
in the concentration of ST was found to increase the swelling and decrease the
shrinking of rubber. From the results of the FTIR
spectrum, DPNR was indicated to be more degraded compared
to DPNR-g-PAN/PS after immersion with DME. The
surface morphology test, which was carried out with a scanning electron
microscope (SEM), showed that DPNR-g-PAN/PS experienced a
slight shrinking effect in its morphology while DPNR underwent a huge shrinking
effect.
Acrylonitrile; Deproteinized natural rubber; Dimethyl ether; Styrene
Dimethyl ether (DME) is
an alternative fuel with several advantages over other fuels, such as higher
oxygen content, a higher cetane number than diesel oil, and a low boiling
point. It is also non-toxic, non-teratogenic, non-mutagenic, and
non-carcinogenic (Semelsberger et al., 2006;
Arcoumanis et al., 2008; Li and
Zhou, 2008).
However, its chemical properties are different from those of LPG, which has
moderate polarity and high gas permeability to organic compounds such as
plastics and rubber; DME swells easily
Furthermore, natural rubber grafted with
acrylonitrile (AN) and styrene (ST) has the potential to be used as a seal for
the storage of DME. It has excellent properties such as good elasticity, high
tensile strength (TS), and good adhesion to metal. Polyacrylonitrile (PAN) is a
non-solvent material with hydrocarbons, chlorinated hydrocarbons ketones,
diethyl ether, and acetonitrile (Mark, 2009).
The presence of PAN could increases its
insolubility and resistance to organic solvents (Nataraj
et al., 2012). ST has also been observed to be a good
co-monomer for the stability of the graft-copolymerization process (Prasassarakich
et al., 2001; Angnanon et al.,
2011; Sari et al., 2015). According to studies conducted by Prasassarakich et al. (2001), the oil and solvent resistance
of Natural Rubber can be
improved by graft copolymerization using AN. Increases in TS and oil resistance
were observed with an increase in the percentage grafting efficiency (GE) of AN
monomer (Prukkaewkanjana et al., 2014);
these results were also reported by Angnanon et al.
(2011).
The objective of the present study was to obtain
a copolymer of DPNR-g-PAN/PS with a high resistance to DME gas. This is
important because resistance is the potency needed by natural rubber to survive
the diffusion or corrosion caused by the DME. According to research conducted
by Sari et al. (2017), the copolymer is
expected to reduce the degradation of rubber because of the action of DME. The
characteristics of the copolymer were determined using Fourier transform infrared
spectroscopy (FTIR). The mechanical properties measured included TS, elongation
at break (EB), and hardness, while the resistance test parameters included
swelling, shrinking, and changes in mechanical properties after immersion. A
surface morphology test was also performed using a
scanning electron microscope (SEM) analysis.
The present study focused on the production and resistance testing
of a DPNR-g-PAN/PS
copolymer in DME with the influence of AN monomer and ST monomer. The presence of AN
and ST increases
the mechanical properties of DPNR and DPNR-g-PAN/PS. It was found that
the lowest percent swelling was attain with the highest of composition of AN,
while the lowest percent of shrinking was attain at the highest of composition
of ST. This condition requires the advance optimization of the AN/ST
composition for swelling and shrinking test. The
FTIR spectrum of DPNR degraded more than that of DPNR-g-PAN/PS spectrum and the morphology of
DPNR-g-PAN/PS experienced a slight shrinking effect while that of DPNR
underwent a huge shrinking
effect.
The authors wish to express their
gratitude to the Research Laboratory of Chemical Engineering FT-UI and the Rubber
Research Center Bogor for their support in this research.
Angnanon, S., Prasassarakich,
P., Hinchiranan, N., 2011. Styrene/Acrylonitrile Graft Natural Rubber as
Compatibilizer in Rubber Blends. Polymer-Plastics
Technology and Engineering, Volume 50(11), pp. 1170–1178
Arcoumanis, C., Bae, C.,
Crookes, R., Kinoshita, E., 2008. The Potential of Di-methyl Ether (DME) as an
Alternative Fuel for Compression-ignition Engines: A Review. Fuel, Volume 87(7), pp. 1014–1030
George, B., Maiti, S.N., Varma,
I.K., 2007. Impact Modification of SAN using NR-g-SAN Copolymers. Journal of Materials Science, Volume
42(19), pp. 8262–8270
Hinchiranan, N., Wannako, P.,
Paosawatyanyong, B., Prasassarakich, P., 2013. 2,2,2-Trifluoroethyl
Methacrylate-graft-natural Rubber: Synthesis and Application as Compatibilizer
in Natural Rubber/Fluoroelastomer Blends. Materials
Chemistry and Physics, Volume 139(2–3), pp. 689–698
Li, G.B., Zhou, L.B., 2008.
Experimental Research on the Resistance of Rubber Materials to Dimethyl Ether. In: Proceedings of the Institution of
Mechanical Engineers, Part D: Journal of Automobile Engineering, Volume 222(6),
pp. 975–978
Luo, P., Wu, G., 2012.
Thermo-mechanical Degradation-induced Grafting of Poly (styrene–acrylonitrile)
to Chlorinated Polyethylene. Polymer
Degradation and Stability, Volume 97(5), pp. 766–770
Mark, J.E., 2009. Polymer Data Handbook. Volume 27, New
York, USA: Oxford University Press
Mark, J.E., Erman, B.,
Roland, C.M., 2013. The Science and
Technology of Rubber. 4th Edition, Boston, Massachusetts, USA:
Academic Press
Mikhailova, G.A., Baburina,
V.A., Kalmykova, V.Y., Deberdeev, R.Y., Kutyrev, G.A., 2009. Effect of
Sorption-inactive Fillers on the Oil and Petrol Resistance of Siloxane Rubbers.
International Polymer Science and
Technology, Volume 36(4), pp. 19–22
Muniandy, K., Ismail, H.,
Othman, N., 2012. Effects of Partial Replacement of Rattan Powder by Commercial
Fillers on the Properties of Natural Rubber Composites. BioResources, Volume 7(4), pp. 4640–4657
Nacimiento, F., Alcántara,
R., González, J.R., Tirado, J.L., 2012. Electrodeposited Polyacrylonitrile and
Cobalt-Tin Composite Thin Film on Titanium Substrate. Journal of The Electrochemical Society, Volume 159(7), pp.
A1028–A1033
Nataraj, S.K., Yang, K.S.,
Aminabhavi, T.M., 2012. Polyacrylonitrile-based Nanofibers—A State-of-the-Art
Review. Progress in Polymer Science,
Volume 37(3), pp. 487–513
Nishimoto, K., Yamamoto, M.,
Omura, A., Sawada, T., Toyota, A., 2011. Dimethyl
Ether-Resistant Rubber Composition. European Patent office, Number EP2348069A1,
pp. 1–10
Prasassarakich, P.,
Sintoorahat, P., Wongwisetsirikul, N., 2001. Enhanced Graft Copolymerization of
Styrene and Acrylonitrile onto Natural Rubber. Journal of Chemical Engineering of Japan, Volume 34(2), pp. 249–253
Prukkaewkanjana, K.,
Kawahara, S., Sakdapipanich, J., 2014. Influence of Reaction Conditions on the
Properties of Nano-matrix Structure Formed by Graft-Copolymerization of
Acrylonitrile onto Natural Rubber. Advanced
Materials Research, Volume 844, pp. 365–368
Pukkate, N., Yamamoto, Y.,
Kawahara, S., 2008. Mechanism of Graft Copolymerization of Styrene onto
Deproteinized Natural Rubber. Colloid and
Polymer Science, Volume 286(4), pp. 411–416
Sahoo, G., Sarkar, N., Swain,
S.K., 2019. Effect of Layered Graphene Oxide on the Structure and Properties of
Bovine Serum Albumin Grafted Polyacrylonitrile Hybrid Bionanocomposites. Polymer Composites, Volume 40(10), pp.
3989–4003
Saputra, A.H., Johan, Sari,
T.I., Cifriadi, A., Maspanger, D.R., Bismo, S., 2016. Degradation
Characteristics of Vulcanized Natural Rubber by Dimethyl Ether Through Filler
and Plasticizer Composition Variations. International
Journal of Technology, Volume 7(4), pp. 616–624
Saputra, A.H., Juneva, S.,
Sari, T.I., Cifriadi, A., 2018. Degradation of Blending Vulcanized Natural
Rubber and Nitril Rubber (NR/NBR) by Dimethyl Ether through Variation of
Elastomer Ratio. In: IOP Conference
Series: Materials Science and Engineering, Volume 345(1), pp. 012035
Sari, T.I., Saputra, A.H.,
Bismo, S., Maspanger, D.R., Cifriadi, A., 2015. The Effect of Styrene Monomer
in the Graft Copolymerization of Acrylonitrile onto Deproteinized Natural
Rubber. International Journal of
Technology, Volume 6(7), pp. 1164–1173
Sari, T.I., Saputra, A. H.,
Maspanger, D.R., Bismo, S., 2017. Modification of Natural Rubber as a Resistant
Material to Dimethyl Ether. Journal of
Applied Sciences, Volume 17(2), pp. 53–60
Semelsberger, T.A., Borup,
R.L., Greene, H.L., 2006. Dimethyl Ether (DME) as an Alternative Fuel. Journal of Power Sources, Volume 156(2),
pp. 497–511
Smith, A.L., 1979. Applied Infrared Spectroscopy: Fundamentals,
Techniques, and Analytical Problem-Solving. Wiley, Hoboken, New Jersey, USA
Suksawad, P., Yamamoto, Y.,
Kawahara, S., 2011. Preparation of Thermoplastic Elastomer from Natural Rubber
Grafted with Polystyrene. European
Polymer Journal, Volume 47(3), pp. 330–337
Wongthong, P., Nakason, C.,
Pan, Q., Rempel, G.L., Kiatkamjornwong, S., 2013. Modification of Deproteinized
Natural Rubber via Grafting Polymerization with Maleic Anhydride. European Polymer Journal, Volume 49(12),
pp. 4035–4046
Wu, N., Zhang, W., Huang, Z.,
2008. Impact of Dimethyl Ether on Engine Seal Materials. Frontiers of Energy and Power Engineering in China, Volume 2(3),
pp. 279–284