The North American market for biodegradable plastics in 2005 was estimated to be
around 60 million pounds (27 kt). Starch-based polymer blends were expected to
account for 30 million pounds (14 kt) with significantly lower growth rates than
other biodegradable polymers such as polyesters. The main hurdle in the growth of
starch-based products is the thermodynamic immiscibility and non-wetting of starch
with other polymers which leads to serious deterioration of mechanical properties at
>25–30 wt% starch. Higher amounts of starch in the blends entail
adding suitable functional groups on starch and other polymers in the blend to make
them more compatible. The primary challenge is to develop fast reaction chemistries
that can be transformed into viable processes and integrated into existing process
lines with economically viable formulations. This article briefly reviews some of
the most promising chemistries available for the reactive extrusion of starch-based
polymer blends (biodegradable/non-biodegradable).
Kalambur, S.
and
Rizvi, S.S.H.
(2005).
Biodegradable and Functionally Superior Starch–Polyester
Nanocomposites from Reactive Extrusion
, J. Appl. Polym. Sci., 96(4):
1072–1082
.
2.
Tatarka, P.D.
and
Cunningham, R.L.
(1998).
Properties of Loose-Fill Foams
, J. Appl. Polym. Sci., 67(7):
1157–1176
.
3.
Chuang, H.K.
and
Han, C.D.
(1985).
Blends of Nylon 6. I. Rheology-structure Relationships
, J. Appl. Polym. Sci., 30(6):
2431–2455
.
4.
Chuang, H.K.
and
Han, C.D.
(1985).
Blends of Nylon 6. II. Propertymorphology Relationships
, J. Appl. Polym. Sci., 30(6):
2457–2474
.
5.
Fontan, E.
,
Chen, C.C.
,
Min, K.
and
White, J.L.
(1988).
An Investigation of Instability of Phase Morphology of Blends of Nylons
with Polyethylenes and Polystyrenes and Effects of Compatibilizing Agents
, Polym. Eng. Sci., 28(2):
69–80
.
6.
Kim, B.K.
and
Park, S.J.
(1991).
Reactive Melt Blending of Nylon with Poly(styrene-co-maleic anhydride)
, J. Appl. Polym. Sci., 43(2):
357–363
.
7.
Choudhury, N.R.
and
Bhowmick, A.K.
(1989).
Compatibilization of Natural Rubber-polyolefin Thermoplastic Elastomeric
Blends by Phase Modification
, J. Appl. Polym. Sci., 38(6):
1091–1109
.
8.
Borggreve, R.J.M.
,
Gaymans, R.J.
and
Schuijer, J.
(1989).
Impact Behavior of Nylon-rubber Blends
, Polymer, 30(1):
71–77
.
9.
Greco, R.
,
Malinconico, M.
,
Martuscelli, E.
,
Ragosta, G.
and
Scarinzi, G.
(1987).
Role of Degree of Grafting of Functionalized Ethylene-propylene Rubber on
the Properties of Rubber-modified Polyamide-6
, Polymer, 28(7):
1185–1189
.
10.
Cimmino, S.
,
Coppola, F.
,
D’Orazio, L.
,
Greco, R.
,
Maglio, G.
,
Malinconico, M.
,
Mancarella, C.
,
Martuscelli, E.
and
Ragosta, G.
(1986).
Ternary Nylon-6/ Rubber/Modified Rubber Blends: Effect of the Mixing
Procedure on Morphology, Mechanical and Impact Properties
, Polymer, 27(12):
1874–1884
.
11.
Cimmino, S.
,
D’Orazio, L.
,
Greco, R.
,
Maglio, G.
,
Malinconico, M.
,
Mancarella, C.
,
Martuscelli, E.
,
Palumbo, R.
and
Ragosta, G.
(1984).
Morphology-properties Relationships in Binary Polyamide 6/Rubber Blends:
Influence of the Addition of a Functionalized Rubber
, Polym. Eng. Sci., 24(1):
48–56
.
Kim, B.K.
,
Park, S.Y.
and
Park, S.J.
(1991).
Morphological, Thermal and Rheological Properties of Blends
Polyethylene/Nylon-6, Polyethylene/ Nylon-6/(maleic
anhydride-g-polyethylene) and (maleic anhydride-gpolyethylene)/Nylon-6
, European Polymer J., 27(4):
349–354
.
14.
Liu, N.C.
,
Baker, W.E.
and
Russell, K.E.
(1990).
Functionalization of Polyethylenes and their use in Reactive Blending
, J. Appl. Polym. Sci., 41(9):
2285–2300
.
15.
Ide, F.
and
Hasegawa, A.
(1974).
Studies on Polymer Blend of Nylon 6 and Polypropylene or Nylon 6 and
Polystyrene using the Reaction of Polymer
, J. Appl. Polym. Sci., 18(4):
963–974
.
16.
Park, S.J.
,
Kim, B.K.
and
Jeong, H.M.
(1990).
Morphological, Thermal and Rheological Properties of Blends
Polypropylene/Nylon-6, Polypropylene/Nylon-6/(maleic
anhydride-g-polypropylene) and (maleic anhydride-g-polypropylene)/Nylon-6
, European Polymer J., 26(2):
131–136
.
17.
Dagli, S.S.
,
Xanthos, M.
and
Biesenberger, J.A.
(1991). Proceedings of the Annual Technical Conference of
SPE, p. 969-969.
18.
Campbell, J.R.
,
Hobbs, S.Y.
,
Shea, T.J.
and
Watkins, V.H.
(1990).
Polyphenylene Oxide/Polyamide Blends via Reactive Extrusion
, Polym. Eng. Sci., 30(17):
1056–1062
.
19.
Carrot, C.
,
Guillet, J.
and
May, J.F.
(1991).
Blends of Polyamide-6 with ABS, Effect of a Compatibilizer on Adhesion and
Interfacial Tension
, Plast. Rubber Compos. Process. Appl., 16:
61–66
.
20.
Angola, J.
,
Fujita, Y.
,
Sakai, T.
and
Inoue, T.
(1988).
Compatibilizer-aided Toughening in Polymer Blends Consisting of Brittle
Polymer Particles Dispersed in a Ductile Polymer Matrix
, J. Polym. Sci., Part B: Polym. Phys.,
26(4):
807–816
.
21.
Triacca, V.J.
,
Ziaee, S.
,
Barlow, J.W.
,
Keskkula, H.
and
Paul, D.R.
(1991).
Reactive Compatibilization of Blends of Nylon-6 and ABS Materials
, Polymer, 32(8):
1401–1413
.
22.
Vaidya, U.R.
and
Bhattacharya, M.
(1994).
Properties of Blends of Starch and Synthetic Polymers Containing Anhydride Groups
, J. Appl. Polym. Sci., 52(5):
617–628
.
23.
Bhattacharya, M.
,
Vaidya, U.R.
,
Zhang, D.
and
Narayan, R.
(1995).
Properties of Blends of Starch and Synthetic Polymers Containing Anhydride
Groups. II. Effect of Amylopectin to Amylose Ratio in Starch
, J. Appl. Polym. Sci., 57(5):
539–554
.
24.
Mani, R.
and
Bhattacharya, M.
(1998).
Properties of Injection Moulded Starch/Synthetic Polymer Blends
–III. Effect of Amylopectin to Amylose Ratio in Starch
, European Polymer J., 34(10):
1467–1475
.
25.
Bhattacharya, M.
,
John, J.
,
Tang, J.
and
Yang, Z.
(1997).
Synthesis and Characterization of Anhydride-functional Polycaprolactone
, J. Polym. Sci., Part A: Polym. Chem.,
35(6):
1139–1147
.
26.
Bhattacharya, M.
,
Mani, R.
and
Tang, J.
(1999).
Functionalization of Polyesters with Maleic Anhydride by Reactive Extrusion
, J. Polym. Sci., Part A: Polym. Chem.,
37(11):
1693–1702
.
27.
Narayan, R.
,
Carlson, D.
,
Nie, L.
and
Dubois, P.
(1999).
Maleation of Polylactide (PLA) by Reactive Extrusion
, J. Appl. Polym. Sci., 72(4):
477–485
.
28.
Mani, R.
and
Bhattacharya, M.
(2001).
Properties of Injection Moulded Blends of Starch and Modified Biodegradable Polyesters
, European Polymer J., 37(3):
515–526
.
29.
Dubois, P.
and
Narayan, R.
(2003).
Biodegradable Compositions by Reactive Processing of Aliphatic
Polyester/Polysaccharide Blends
, Macromolecular Symp., 198(1):
233–243
.
30.
Avella, M.
,
Errico, M.E.
,
Rimedio, R.
and
Sadocco, P.
(2002).
Preparation of Biodegradable Polyesters/High-amylose Starch Composites by
Reactive Blending and their Characterization
, J. Appl. Polym. Sci., 83(7):
1432–1442
.
31.
Liu, N.C. and Baker, W.E. (1991). POLYBLENDS-91, Montreal, Canada, October 1991.
32.
Fowler, M.W.
and
Baker, W.E.
(1988).
Rubber Toughening of Polystyrene through Reactive Blending
, Polym. Eng. Sci., 28(21):
1427–1433
.
33.
Chen, B.S.Y. and Henton, D.E. (1989). Functionalized Elastomers Blended with
Polar Copolymers of Styrene and Acrylic Acid Methacrylic Acid or Maleic Anhydride,
US Patent# 4,886,856.
34.
Bhattacharya, M.
,
John, J.
and
Tang, J.
(1998).
Grafting of Oxazoline Functional Group to Polycaprolactone
, J. Appl. Polym. Sci., 67(11):
1947–1955
.
35.
Jane, J.L., Schwabacher, A.W., Ramrattan, S.N. and Moore, J.A. (1992).
Biodegradable Starch Plastics Incorporating Modified Polyethylene, US Patent# 5,115,000.
36.
Innocentini-Mei, L.H.
,
Bartoli, J.R.
and
Baltieri, R.C.
(2003).
Mechanical and Thermal Properties of Poly(3-hydroxybutyrate) Blends with
Starch and Starch Derivatives
, Macromolecular Symp., 197(1):
77–87
.
37.
Narayan, R.
,
Krishnan, M.
and
Dubois, P.
(1999).
Aliphatic Polyestergrafted Starch-like Polysaccharides by Ring-opening Polymerization
, Polymer, 40(11):
3091–3100
.
38.
Narayan, R., Krishnan, M., Snook, J.B., Gupta, A. and DuBois, P. (1999). Bulk
Reactive Extrusion Polymerization Process Producing Aliphatic Ester Polymer
Compositions, US Patent# 5,969,089.
39.
Narayan, R., Krishnan, M., Snook, J.B., Gupta, A. and DuBois, P. (1999). Bulk
Reactive Extrusion Polymerization Process Producing Aliphatic Ester Polymer
Compositions, US Patent# 5,906,783.
40.
Narayan, R., Krishnan, M., Snook, J.B., Gupta, A. and DuBois, P. (1999). Bulk
Reactive Extrusion Polymerization Process Producing Aliphatic Ester Polymer
Compositions, US Patent# 5,801,224.
41.
De Graff, R.A.
and
Janssen, L.P.B.M.
(2000).
The Production of new Partially Biodegradable Starch Plastic by Reactive Extrusion
, Polym. Eng. Sci., 40(9):
2086–2094
.
42.
Bagley, E.B.
,
Fanta, G.F.
,
Burr, R.C.
,
Doane, W.M.
and
Russell, C.R.
(1977).
Graft Copolymers of Polysaccharides with Thermoplastic Polymers. A New Type
of Filled Plastic
, Polym. Eng. Sci., 17(5):
311–316
.
43.
Fanta, G.F.
,
Trimnell, D.
and
Salch, J.H.
(1993).
Graft Polymerization of Methyl Acrylate-vinyl Acetate Mixtures onto Starch
, J. Appl. Polym. Sci., 49(9):
1679–1682
.
44.
Tahan, M.
and
Zilkha, A.
(1969).
Anionic Graft Polymerization of Ethylene Oxide on Starch. I
, J. Polym. Sci., Part A1, 7:
1815–1824
.
45.
Tahan, M.
and
Zilkha, A.
(1969).
Anionic Graft Polymerization of Ethylene Oxide on Starch. II
, J. Polym. Sci., Part A1, 7:
1825–1837
.
Pledger, Jr., H.
,
Young, T.S.
,
Wu, G.S.
,
Butler, G.B.
and
Hoegen-Esch, T.E.
(1985).
Synthesis and Characterization of Water-soluble Starch-Acrylamide Graft Copolymers
, J. of Macromol. Sci. Chem., A22(4):
415–436
.
48.
Kalambur, S.
and
Rizvi, S.S.H.
(2004).
Starch-based Nanocomposites by Reactive Extrusion Processing
, Polym. Int., 53(10):
1413–1416
.
