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Starch Formates: Synthesis and Modification molecules Article Starch Formates: Synthesis and Modification Sascha Blohm 1, Thomas Heinze 1,* and Haisong Qi 2 1 Centre of Excellence for Polysaccharide Research, Institute for Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstraße 10, D-07743 Jena, Germany; [email protected] 2 State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China; [email protected] * Correspondence: [email protected]; Tel.: +49-3641-948270 Abstract: Starch can be efficiently converted into the corresponding formates homogeneously using N-formyl imidazole obtained by the reaction of 1,10-carbonyldiimidazole and formic acid in dimethyl sulfoxide as a solvent. Starch formates are soluble in polar aprotic solvents, not susceptible against hy- drolysis, and not meltable. Thermoplastics could be generated by conversion of starch formates with long-chain fatty acids exemplified by the conversion with lauroyl chloride in N,N-dimethylacetamide, leading to mixed starch laurate formates. The mixed esters show melting temperatures mainly dependent on the amount of laurate ester moieties. Keywords: starch; esterification; starch formate; mixed starch ester; thermoplastic 1. Introduction Polysaccharide esters play an important role in various fields of application, e.g., as Citation: Blohm, S.; Heinze, T.; Qi, H. foils, films, filters, and thermoplastic to replace plastics based on fossil resources. Thermo- Starch Formates: Synthesis and plastic starch may be obtained by derivatisation with long-chain fatty acids that yields a Modification. Molecules 2021, 26, 4882. disturbance of the intra- and intermolecular hydrogen bonds of the polysaccharide [1–3]. https://doi.org/10.3390/molecules While polysaccharide esters of a broad variety of carboxylic acids are known and even 26164882 commercially produced, the formic acid ester is scarcely investigated up until now. It was shown that organo-soluble formates of cellulose could be easily synthesised and used for Academic Editors: Janusz Kapusniak esterification with other carboxylic acids [4]. Moreover, formic acid is able to dissolve and Idalina Gonçalves carboxymethyl cellulose by acylation of the remaining hydroxyl groups [5]. Starch formate was obtained by the reaction of starch with formic acid [6–15]. How- Received: 21 July 2021 ever, the reaction is highly sensitive even to traces of water [8] and leads to starch formate Accepted: 11 August 2021 with low average degrees of substitution (DS) only [6,7,10]. Up to now, the highest DS Published: 12 August 2021 value of starch formate known was 2.14 and was reached at extended reaction time, high temperature, with extensively dried starch, and the use of a high excess of concentrated Publisher’s Note: MDPI stays neutral formic acid [8]. Unfortunately, on one hand, both formic acid chloride and -anhydride with regard to jurisdictional claims in are difficult to handle under usual conditions. On the other hand, the reaction of formic published maps and institutional affil- acid with 1,10-carbonyldiimidazole (CDI) has been described, resulting in N-formyl imida- iations. zole [16]. N-formyl imidazole is stable up to about 60 ◦C and rather sensitive to hydrolysis. Nevertheless, it is highly reactive concerning alcohols. Thus, in the present study, it was investigated to prepare a formic acid ester of starch with a high degree of substitution (DS), applying N-formyl imidazole. Moreover, the properties of the starch formates, including Copyright: © 2021 by the authors. subsequent esterification, were studied. Licensee MDPI, Basel, Switzerland. This article is an open access article 2. Results distributed under the terms and A mixture of formic acid and 1,10-carbonyldiimidazole (CDI) was allowed to react in conditions of the Creative Commons dimethyl sulfoxide (DMSO) to form the N-formyl imidazole. Subsequently, the N-formyl Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ imidazole was added to a solution of starch (1) in DMSO at an elevated temperature 4.0/). (Figure1). Molecules 2021, 26, 4882. https://doi.org/10.3390/molecules26164882 https://www.mdpi.com/journal/molecules Molecules 2021, 26, x FOR PEER REVIEW 2 of 8 Molecules 2021, 26, 4882 2 of 8 imidazole was added to a solution of starch (1) in DMSO at an elevated temperature (Fig- ure 1). FigureFigure 1. 1. SchemeScheme for for the the reaction reaction of of starch starch ( (11)) with with formic formic acid acid and and 1,1 1,1′0-carbonyldiimidazole-carbonyldiimidazole yielding yielding NN-formyl-formyl imidazole imidazole inin dimethyl dimethyl sulfoxide. sulfoxide. 2.1.2.1. Synthesis Synthesis and and Characteri Characterisationsation of of Starch Starch Formates Formates StarchStarch formate samplessamples withwith degrees degrees of of substitution substitution (DS) (DS) in thein the range range from from 0.97 0.97 to 2.55 to 2.55(16 h(16 reaction h reaction time) time) could could be obtained be obtained by the by reaction the reaction shown shown in Figure in1 .Figure A high 1. DS A couldhigh DS be couldrealised be byrealised applying by aapplying fivefold a excess fivefold of formic excess acid of formic and CDI acid related and CDI to the related anhydroglucose to the an- hydroglucoseunit (AGU), even unit within(AGU), a 3-heven reaction within timea 3-hour at 60 reaction◦C (Table time1). Up at to60 now,°C (Table the highest 1). Up DS to now,value the of starchhighest formate DS value known of starch was 2.14 formate and was known reached was at 2.14 an extended and was reactionreached time, at an high ex- tendedtemperature, reaction with time, extensively high temperature, dried starch, with and extensively the use of dried a high starch, excess and of concentrated the use of a highformic excess acid of [8 concentrated]. Other attempts formic published acid [8]. Other in the attempts literature published with less in concentrated the literature formic with lessacid concentrated or less dried formic starch ledacid to or a less limitation dried starch of the DSled ofto abouta limitation 1. of the DS of about 1. The starch formates obtained in the present studies were characterised by means of FTIR-Table 1.andConditions NMR spectroscopic for and results measurements. of the reactions of A starch typical (1) withFTIRN spectrum-formyl imidazole of sample obtained 2d, in- by 0 cludingthe conversion the signal of formic assignments, acid and 1,1 is -carbonyldiimidazoleshown in Figure 2. inThe dimethyl vibrational sulfoxide. bands of the intra- and intermolecular O-H bonds Reactionare not particular Conditionsly intense, which fits the Starch high Formate DS of the sample.Sample On the contrary, the dominant band of the carbonyl vibration is clearly visible at Temp. Molar Ratio Time Efficiency 1727 cmNo.−1, which is a typical value for formic acid esters [17]. DS [◦C] AGU:Formic Acid:CDI [h] [%] Table 1.2a Conditions for60 and results of the reactions 1:1:1 of starch (1) with 3 N-formyl 0.97 imidazole obtained 97 by the conversion2b of formic60 acid and 1,1′-carbonyldiimidazole 1:2:2 in dimethyl 3 sulfoxide. 1.86 93 2c 60 1:3:3 3 2.15 72 2d 60Reaction Conditions 1:5:5 3 2.44Starch Formate 49 Sample 2e Temp. 50Molar 1:3:3Ratio Time 3 1.99Efficiency 66 No.2f 50 1:5:5 16DS 2.55 51 [°C] AGU:Formic Acid:CDI [h] [%] 2a 60 1:1:1 3 0.97 97 2bThe starch60 formates obtained1:2:2 in the present studies were3 characterised1.86 by93 means of FTIR- and NMR spectroscopic measurements. A typical FTIR spectrum of sample 2d, 2c 60 1:3:3 3 2.15 72 including the signal assignments, is shown in Figure2. The vibrational bands of the intra- 2d 60 1:5:5 3 2.44 49 and intermolecular O-H bonds are not particularly intense, which fits the high DS of the 2e 50 1:3:3 3 1.99 66 sample. On the contrary, the dominant band of the carbonyl vibration is clearly visible at 17272f cm −1, which50 is a typical value for1:5:5 formic acid esters [1716]. 2.55 51 The 13C NMR spectra of starch formate samples of different DS values are displayed 13 in FigureThe 3.C The NMR signals spectra of the of starch AGU are formate found samples in the range of different of 60–100 DS ppm. values For are sample displayed2a of inthe Figure lowest 3. DS The value, signals there of the is only AGU one are signal found visible in the at range 99.95 of ppm 60–100 for position ppm. For 1 of sample the AGU 2a ofwithout the lowest an esterified DS value, neighboring there is only position one sign 2.al The visible signal at at99.95 79.00 ppm ppm for can position be assigned 1 of the to AGUposition without 4. The an signals esterified for carbon neighboring atoms 2position and 3 without 2. The substituentssignal at 79.00 and ppm those can of carbonbe as- signedatom 5 to can position be observed 4. Theat signals 73.11 ppm,for carbon 71.56 atoms ppm, and2 and 69.94 3 without ppm, respectively. substituents and those of carbon atom 5 can be observed at 73.11 ppm, 71.56 ppm, and 69.94 ppm, respectively. Molecules 2021, 26, 4882 3 of 8 Molecules 2021, 26, x FOR PEER REVIEW 3 of 8 FigureFigure 2.2. FTIRFTIR spectrumspectrum (KBr,(KBr, resolutionresolution 11 cmcm−−1,, 64 64 scans) scans) of of starch starch formate formate 2d (degree(degree of substitution = 2.44). 2.44). Position 3 with esterified position 2 adjacent is represented by the signal at 68.35 ppm. The signals at 62.85 ppm and 60.38 ppm can be assigned to position 6, which is esterified and unchanged.
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