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. 2021 May 7;13(9):1504.
doi: 10.3390/polym13091504.

Production of Cyclic Anhydride-Modified Starches

Ryan C Amos  1 , Julien Mesnager  2 , Michael Kuska  2 , Mario Gauthier  1
Affiliations

Production of Cyclic Anhydride-Modified Starches

Ryan C Amos et al. Polymers (Basel). .

Abstract

Modified starches offer a biodegradable, readily available, and cost-effective alternative to petroleum-based products. The reaction of alkenylsuccinic anhydrides (ASAs), in particular, is an efficient method to produce amphiphilic starches with numerous applications in different areas. While ASAs are typically derived from petroleum sources, maleated soybean oil can also be used in an effort to produce materials from renewable sources. The reaction of gelatinized waxy maize starch with octenylsuccinic anhydride (OSA), dodecenylsuccinic anhydride (DDSA), a maleated fatty acid (TENAX 2010), phthalic anhydride (PA), 1,2,4-benzenetricarboxylic acid anhydride (trimellitic anhydride, TMA), and three maleated soybean oil samples, was investigated under different conditions. To minimize the reaction time and the amount of water required, the outcome of the esterification reaction was compared for starch dispersions in benchtop dispersed reactions, for starch melts in a heated torque rheometer, and for reactive extrusion in a pilot plant scale twin-screw extruder. The extent of reaction was quantified by 1H NMR analysis, and changes in molecular weight and diameter were monitored by gel permeation chromatography (GPC) analysis. The outcome of the reactions varied markedly in terms of reaction efficiency (RE), molecular weight distribution, and average hydrodynamic diameter, for the products derived from the different maleated reagents used, as well as for the different reaction protocols.

Keywords: alkenylsuccinic anhydride (ASA); esterification; reactive extrusion; soybean oil; starch.

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Conflict of interest statement

Julien Mesnager and Michael Kuska were employed by EcoSynthetix during the investigation. Ryan C. Amos and Mario Gauthier declare no conflict of interest.

Figures

Figure 1
Figure 1
Chemical structure of (A) amylose and (B) amylopectin.
Figure 2
Figure 2
Chemical structure of (A) OSA, (B) DDSA, (C) phthalic anhydride, (D) 1,2,4-benzenetricarboxylic acid anhydride, (E) TENAX 2010, and (F) maleated soybean oil with one equivalent of maleic anhydride (many isomers possible).
Scheme 1
Scheme 1
Reaction of starch with OSA. The ester is drawn in the C2 position, but esterification is possible at C2, C3 or C6.
Figure 3
Figure 3
Modification of starch with (A) OSA and (B) DDSA. Conversion at different weight loadings for (▲) gelatinized starch dispersions, (□) melt mixer reactions without base, and (■) melt mixer reactions with base.
Figure 4
Figure 4
Typical torque variation at 90 °C and 40 rpm for starch with water (formula image) and starch with water and OSA (formula image).
Figure 5
Figure 5
Modification of starch with (A) PA and (B) TMA. Reaction efficiency at different weight loadings for (▲) dispersed starch, (□) melt mixer reactions without base, (■) melt mixer reactions with 1.1 equiv of NaOH, and (x) melt mixer reactions with 2.2 equiv of NaOH.
Figure 6
Figure 6
Modification of starch with (A) TENAX 2010, (B) MSO-1.1, (C) MSO-2.2, and (D) MSO-2.3. Conversion at different weight loadings for (▲) dispersed starch and melt mixer reactions (□) without and (■) with base.
Figure 7
Figure 7
Typical torque curves at 90 °C and 60 rpm for starch with water (formula image), and for starch, water and MSO-2.0 without base (formula image) and with base (formula image).
Figure 8
Figure 8
Modification of starch in a pilot plant twin-screw extruder (□) without base and (■) with 1.1 equiv of NaOH and (A) DDSA, (B) TENAX 2010, and (C) MSO-1.1.
See this image and copyright information in PMC

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