Synthesis and Properties of Biobased Polyurethane/Montmorillonite Nanocomposites
Polyurethanes (PURs) are very versatile polymeric
materials with a wide range of physical and chemical properties.
PURs have desirable properties such as high abrasion resistance, tear
strength, shock absorption, flexibility and elasticity. Although they
have relatively poor thermal stability, this can be improved by using
treated clay. Polyurethane/clay nanocomposites have been
synthesized from renewable sources. A polyol for the production of
polyurethane by reaction with an isocyanate was obtained by the
synthesis of palm oil-based oleic acid with glycerol. Dodecylbenzene
sulfonic acid (DBSA) was used as catalyst and emulsifier. The
unmodified clay (kunipia-F) was treated with cetyltrimethyl
ammonium bromide (CTAB-mont) and octadodecylamine (ODAmont).
The d-spacing in CTAB-mont and ODA-mont were 1.571 nm
and 1.798 nm respectively and larger than that of the pure-mont
(1.142 nm). The organoclay was completely intercalated in the
polyurethane, as confirmed by a wide angle x-ray diffraction
(WAXD) pattern.
The results showed that adding clay demonstrated better thermal
stability in comparison with the virgin polyurethane. Onset
degradation of pure PU is at 200oC, and is lower than that of the
CTAB-mont PU and ODA-mont PU which takes place at about
318oC and 330oC, respectively. The mechanical properties (including
the dynamic mechanical properties) of pure polyurethane (PU) and
PU/clay nanocomposites, were measured. The modified organoclay
had a remarkably beneficial effect on the strength and elongation at
break of the nanocomposites, which both increased with increasing
clay content with the increase of the tensile strength of more than
214% and 267% by the addition of only 5 wt% of the
montmorillonite CTAB-mont PU and ODA-mont PU, respectively.
[1] Rihayat, T., Saari, M., Mahmood, M.H., Wan Yunus, W.M.Z., Suraya,
A.R., Dahlan, K. Z. H. M. and Sapuan, S.M.. 2006. Synthesis and
thermal characterization of Polyurethane/ clay nanocomposites based
on palm oil polyol. Polymer Plastics Technology and Engineering 45 :
1323-1326
[2] Warwel, S., Bruse, F., Demes, C., Kunz, M, and Klaas, M.R. 2001.
Polymers and surfactants on the basis of renewable resources.
Chemosphere 43: 39-48
[3] Guo, A., Demydov, D., Zhang, W. and Petrovic, Z.S. 2002. Polyols and
Polyurethanes from Hydroformylation of Soybean Oil, Journal of
Polymers and the Environment 10: 49-52
[4] Beuer, B., Gruetzmacher, R., Heidbreder, A. and Klein, J. 2000.
Polyurethane resins. US Patent no. 6,046,298.
[5] Bierman, U., Friedt, W., Lang, S., Luhs, W., Machmuller, G., Metzger,
J.O., Klass, M.R., Schafer, H.J., and Scheiner, M.P. 2000. New
synthesis with oils and fats as renewable raw materials for the chemical
industry. Angew.Chem.Int.ed. 39 : 2206 - 2224.
[6] Nakamura, K., Nishimura, Y., Zetterlund, P., Hatakeyama, T. and
Hatakeyama, H. 1996. TG-FTIR studies on biodegradable
polyurethanes containing mono-and disaccharide components.
Thermochimica acta 282/283 : 433-441.
[7] Petrovic, Z.S and Ferguson, J. 1991. Polyurethane elastomers.
Prog.Polym.Sci.16 : 695-836.
[8] Zapletalova, T., Michielsen, S. and Pourcheyhimi, B. 2006. Polyether
based thermoplastic polyurethane melt blown nonwovens. Journal of
Engineered Fibers and Fabrics 1 : 62-72.
[9] Alexandre, M and Dubois, P. 2000. Polymer-layered silicate
nanocomposites: preparation, properties and uses of a new class of
materials. Materials Science and Engineering: R: Reports 28: 1-63
[10] Eychenne, V. and Mouloungui, Z. 1999. High concentration of 1-(3-
)monoglycerides by direct partial esterification of fatty acids with
glycerol. Fett/Lipid 101 : 424-427
[11] Chen, T.K., Tien, Y.I. and Wei, K.H. 2000. Synthesis and
characterization of novel segmented polyurethane/clay nanocomposites.
Polymer 41: 1345-1353
[12] Chun, B.C., Cho, T.K., Chung, Y.C. 2006. Enhanced mechanical and
shape memory properties of polyurethane block copolymers chainextended
by ethylene diamines. European Polymer Journal 42 : 3367-
3373
[13] Rihayat, T., Saari, M., Hilmi Mahmood, M., Wan Yunus, W.M.Z.,
Suraya, A.R., Dahlan, K,Z.H.M. and Sapuan, S.M. 2007. Mechanical
Characterisation of Polyurethane/Clay Nanocomposites. Polymers &
Polymer Composites 15: 597-602
[14] Abdalla, M.O., Dean, D. and Campbell, S. 2002. Viscoelastic and
mechanical properties of thermoset PMR-type polyimide-clay
nanocomposites. Polymer 43: 5887
[15] Choi, W.J., Kim, S.H., Kim, Y.J. and Kim, S.C. 2004. Synthesis of
chain-extended organifier and properties of polyurethane/clay
nanocomposites. Polymer 45: 6045-6057
[16] Agag, T., Koga, T. and Takeichi, T. 2001. Studies on thermal and
mechanical properties of polyimide-clay nanocomposites. Polymer 42:
3399-3408.
[1] Rihayat, T., Saari, M., Mahmood, M.H., Wan Yunus, W.M.Z., Suraya,
A.R., Dahlan, K. Z. H. M. and Sapuan, S.M.. 2006. Synthesis and
thermal characterization of Polyurethane/ clay nanocomposites based
on palm oil polyol. Polymer Plastics Technology and Engineering 45 :
1323-1326
[2] Warwel, S., Bruse, F., Demes, C., Kunz, M, and Klaas, M.R. 2001.
Polymers and surfactants on the basis of renewable resources.
Chemosphere 43: 39-48
[3] Guo, A., Demydov, D., Zhang, W. and Petrovic, Z.S. 2002. Polyols and
Polyurethanes from Hydroformylation of Soybean Oil, Journal of
Polymers and the Environment 10: 49-52
[4] Beuer, B., Gruetzmacher, R., Heidbreder, A. and Klein, J. 2000.
Polyurethane resins. US Patent no. 6,046,298.
[5] Bierman, U., Friedt, W., Lang, S., Luhs, W., Machmuller, G., Metzger,
J.O., Klass, M.R., Schafer, H.J., and Scheiner, M.P. 2000. New
synthesis with oils and fats as renewable raw materials for the chemical
industry. Angew.Chem.Int.ed. 39 : 2206 - 2224.
[6] Nakamura, K., Nishimura, Y., Zetterlund, P., Hatakeyama, T. and
Hatakeyama, H. 1996. TG-FTIR studies on biodegradable
polyurethanes containing mono-and disaccharide components.
Thermochimica acta 282/283 : 433-441.
[7] Petrovic, Z.S and Ferguson, J. 1991. Polyurethane elastomers.
Prog.Polym.Sci.16 : 695-836.
[8] Zapletalova, T., Michielsen, S. and Pourcheyhimi, B. 2006. Polyether
based thermoplastic polyurethane melt blown nonwovens. Journal of
Engineered Fibers and Fabrics 1 : 62-72.
[9] Alexandre, M and Dubois, P. 2000. Polymer-layered silicate
nanocomposites: preparation, properties and uses of a new class of
materials. Materials Science and Engineering: R: Reports 28: 1-63
[10] Eychenne, V. and Mouloungui, Z. 1999. High concentration of 1-(3-
)monoglycerides by direct partial esterification of fatty acids with
glycerol. Fett/Lipid 101 : 424-427
[11] Chen, T.K., Tien, Y.I. and Wei, K.H. 2000. Synthesis and
characterization of novel segmented polyurethane/clay nanocomposites.
Polymer 41: 1345-1353
[12] Chun, B.C., Cho, T.K., Chung, Y.C. 2006. Enhanced mechanical and
shape memory properties of polyurethane block copolymers chainextended
by ethylene diamines. European Polymer Journal 42 : 3367-
3373
[13] Rihayat, T., Saari, M., Hilmi Mahmood, M., Wan Yunus, W.M.Z.,
Suraya, A.R., Dahlan, K,Z.H.M. and Sapuan, S.M. 2007. Mechanical
Characterisation of Polyurethane/Clay Nanocomposites. Polymers &
Polymer Composites 15: 597-602
[14] Abdalla, M.O., Dean, D. and Campbell, S. 2002. Viscoelastic and
mechanical properties of thermoset PMR-type polyimide-clay
nanocomposites. Polymer 43: 5887
[15] Choi, W.J., Kim, S.H., Kim, Y.J. and Kim, S.C. 2004. Synthesis of
chain-extended organifier and properties of polyurethane/clay
nanocomposites. Polymer 45: 6045-6057
[16] Agag, T., Koga, T. and Takeichi, T. 2001. Studies on thermal and
mechanical properties of polyimide-clay nanocomposites. Polymer 42:
3399-3408.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:55324", author = "Teuku Rihayat and Suryani", title = "Synthesis and Properties of Biobased Polyurethane/Montmorillonite Nanocomposites", abstract = "Polyurethanes (PURs) are very versatile polymeric
materials with a wide range of physical and chemical properties.
PURs have desirable properties such as high abrasion resistance, tear
strength, shock absorption, flexibility and elasticity. Although they
have relatively poor thermal stability, this can be improved by using
treated clay. Polyurethane/clay nanocomposites have been
synthesized from renewable sources. A polyol for the production of
polyurethane by reaction with an isocyanate was obtained by the
synthesis of palm oil-based oleic acid with glycerol. Dodecylbenzene
sulfonic acid (DBSA) was used as catalyst and emulsifier. The
unmodified clay (kunipia-F) was treated with cetyltrimethyl
ammonium bromide (CTAB-mont) and octadodecylamine (ODAmont).
The d-spacing in CTAB-mont and ODA-mont were 1.571 nm
and 1.798 nm respectively and larger than that of the pure-mont
(1.142 nm). The organoclay was completely intercalated in the
polyurethane, as confirmed by a wide angle x-ray diffraction
(WAXD) pattern.
The results showed that adding clay demonstrated better thermal
stability in comparison with the virgin polyurethane. Onset
degradation of pure PU is at 200oC, and is lower than that of the
CTAB-mont PU and ODA-mont PU which takes place at about
318oC and 330oC, respectively. The mechanical properties (including
the dynamic mechanical properties) of pure polyurethane (PU) and
PU/clay nanocomposites, were measured. The modified organoclay
had a remarkably beneficial effect on the strength and elongation at
break of the nanocomposites, which both increased with increasing
clay content with the increase of the tensile strength of more than
214% and 267% by the addition of only 5 wt% of the
montmorillonite CTAB-mont PU and ODA-mont PU, respectively.", keywords = "Polyurethane, Clay nanocomposites, Biobase", volume = "4", number = "5", pages = "315-5", }