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On the Para/Ortho Reactivity of Isocyanate Groups during the Carbamation of Cellulose Nanocrystals Using 2,4-Toluene Diisocyanate

Fraunhofer Institute for Wood Research (WKI), Bienroder Weg 54E, 38108 Braunschweig, Germany
Polymers 2019, 11(7), 1164;
Received: 18 June 2019 / Revised: 4 July 2019 / Accepted: 5 July 2019 / Published: 8 July 2019
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2,4-toluene diisocyanate (TDI) has been commonly used to bind molecules and polymers onto the surface of cellulose nanocrystals (CNCs). Such a process usually involves two steps: (1) the more reactive para-isocyanates (p-NCOs) of TDI are reacted with the surface hydroxyl groups of CNCs then (2) the ortho-isocyanates (o-NCOs) are reacted with certain desired molecules. During the first reaction, an ideal para/ortho selectivity could be impossible to achieve, as o-NCOs are not fully unreactive. Therefore, there is a need to better understand the reaction between CNCs and TDI towards a maximum para/ortho selectivity. For that goal, CNCs were reacted with TDI under varying temperatures (35–75 °C) and TDI/CNCs molar ratios (1–5). The amount of the reacted TDI was estimated using elemental analysis while the free o-NCO groups were quantified following the hydrolysis method of Abushammala. The results showed that temperature had a negative impact on para/ortho selectivity while TDI/CNCs molar ratio improved it. A maximum selectivity of 93% was achieved using a temperature of 35 °C and a molar ratio of 3. This is a three-fold improvement to that using the traditional reaction conditions (75 °C and molar ratio of 1). View Full-Text
Keywords: cellulose; nanocellulose; toluene diisocyanate; isocyanate; carbamation cellulose; nanocellulose; toluene diisocyanate; isocyanate; carbamation

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Abushammala, H. On the Para/Ortho Reactivity of Isocyanate Groups during the Carbamation of Cellulose Nanocrystals Using 2,4-Toluene Diisocyanate. Polymers 2019, 11, 1164.

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