A Simple Method for the Quantification of Free Isocyanates on the Surface of Cellulose Nanocrystals upon Carbamation using Toluene Diisocyanate

Abushammala, Hatem

doi:10.3390/surfaces2020032

Cited by 23 publications

(24 citation statements)

References 29 publications

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“…Earlier, it has been shown by the author that the CNCs used in this paper have ca. 7.5% of their total hydroxyl groups available on the surface for a possible chemical modification [22]. The author has also optimized the reaction of these CNCs with TDI towards reacting all surface hydroxyl groups selectively with the para isocyanate of TDI [23].…”

Section: Resultsmentioning

confidence: 99%

“…Since then, the reaction has more often been used to graft functional molecules and polymers onto nanocellulose surfaces [21]. The reaction was only recently optimized to react all the CNC surface hydroxyls with TDI molecules, most of which have their orthoisocyanates available for a further reaction with certain functional molecules [22,23].…”

Section: Introductionmentioning

confidence: 99%

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Nano-Brushes of Alcohols Grafted onto Cellulose Nanocrystals for Reinforcing Poly(Butylene Succinate): Impact of Alcohol Chain Length on Interfacial Adhesion

Abushammala

2020

Polymers

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Despite the many interesting properties of cellulose nanocrystals (CNCs), their hydrophilicity is one of the main challenges for their processing with hydrophobic polymers and matrices. To overcome this challenge, this paper describes the preparation of brush-like CNCs with tailored surface properties by grafting alcohols of different chain lengths onto their surfaces. Ethanol, 1-butanol, 1-hexanol, and 1-octanol were grafted on the CNC surface using 2,4-toluene diisocyanate (TDI) as a linker. The CNCs were characterized for their structural, morphological, surface, and thermal properties. Because of the grafting, the water contact angle of the CNCs significantly increased from 32° to up to 120°, which was dependent on the chain length of the grafted alcohol. The thermal stability of the CNCs was also improved, mainly as a result of the reaction of TDI with the CNC hydroxyl groups. Later, the CNCs were used to reinforce films of poly(butylene succinate) (PBS), which were then characterized using dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). An increase of up to two-fold in the storage modulus was observed using DMA, which was dependent on the chain length of the grafted alcohol. However, no change in the glass transition temperature or degradation temperature of PBS was detected. This approach is proved efficient for tailoring the surface properties of CNCs towards excellent interfacial adhesion in their composites.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nano-Brushes of Alcohols Grafted onto Cellulose Nanocrystals for Reinforcing Poly(Butylene Succinate): Impact of Alcohol Chain Length on Interfacial Adhesion

Abushammala

2020

Polymers

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“…The isocyanate can react further with water to form carbamic acid in R2 followed by its decomposition to yield the amine derivative in R3. The reactions R2 and R3 are well-known reactions in polyurethane chemistry that are used in the process of making polyurethane foams [ 22 , 23 , 24 ]. Furthermore, it is also assumed that the rate-determining step to form amine from isocyanate is due to the reaction of isocyanate with water (R2) and the decomposition of the formed carbamic acid to amine is a relatively fast process.…”

Section: Resultsmentioning

confidence: 99%

Conversion of Isocyanide to Amine in The Presence of Water and Hg(II) Ions: Kinetics and Mechanism as Detected by Fluorescence Spectroscopy and Mass Spectrometry

Adamoczky

Nagy

et al. 2020

IJMS

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Aromatic isocyanides including isocyanonaphthalene derivatives have been proven to be very effective fluorescent sensors for the quantification of Hg(II) ions in water. Thus, the reaction of 1,5-isocyanoaminonaphthalene (1,5-ICAN), which is one of the most important members of this family, with water and HgCl2 as the oxidation agents, was studied by fluorescence spectroscopy and mass spectrometry in order to get deeper insight into the kinetics and mechanistic details of this complex reaction. The reactions of 1,5-ICAN with water and HgCl2 were performed in various water/co-solvent mixtures of different compositions. The co-solvents used in this study were both aprotic solvents including tetrahydrofuran, acetonitrile and N,N-dimethylformamide and protic solvents, such as ethanol and 2-propanol. It was found that in aprotic solvents the conversion of the isocyano group to amino moiety takes place, while in protic solvents the corresponding carbamate (urethane) group is formed in addition to the amino moiety. The variation of the resulting fluorescence intensities versus time curves were described using an irreversible, consecutive reaction model, in which the formation of isocyanate and carbamic acid intermediates, as well as diamino and carbamate (in the case of protic solvents) products were assumed. The formation of these intermediates and products was unambiguously confirmed by mass spectrometric measurements. Furthermore, by fitting the model to the experimental fluorescence versus time curves, the corresponding rate coefficients were determined. It was observed that the overall rate of transformation of the isocyano group to amino moiety increased with the water concentration and the polarity of the co-solvent. It was also supported that formation of diamino and carbamate derivatives in protic solvents takes place simultaneously and that the ratio of the amino to the carbamate function increased with the increasing water concentration. In addition, with an extension, the model presented herein proved to be capable of describing the kinetics of the transformation of 1,5-diisocyanonaphthalene (1,5-DIN) into 1,5-diaminonaphthalene (1,5-DAN) in the mixtures of water/aprotic solvents.

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“…The degree of substitution of isocyanates (DS NCO ) was determined following the method of Abushammala [23] (see the Supplementary Materials).…”

Section: Methodsmentioning

confidence: 99%

“…In a previous report, the author has developed a simple method for quantifying the isocyanates (o-NCO) available on the CNC surface upon TDI-based carbamation [23]. It relies on the pH increase upon hydrolyzing the free isocyanates of the carbamated CNCs using HCl-acidified dimethyl sulfoxide (DMSO) as a hydrolysis medium.…”

Section: Introductionmentioning

confidence: 99%

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

Abushammala

2019

Polymers

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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).

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A Simple Method for the Quantification of Free Isocyanates on the Surface of Cellulose Nanocrystals upon Carbamation using Toluene Diisocyanate

Cited by 23 publications

References 29 publications

Nano-Brushes of Alcohols Grafted onto Cellulose Nanocrystals for Reinforcing Poly(Butylene Succinate): Impact of Alcohol Chain Length on Interfacial Adhesion

Nano-Brushes of Alcohols Grafted onto Cellulose Nanocrystals for Reinforcing Poly(Butylene Succinate): Impact of Alcohol Chain Length on Interfacial Adhesion

Conversion of Isocyanide to Amine in The Presence of Water and Hg(II) Ions: Kinetics and Mechanism as Detected by Fluorescence Spectroscopy and Mass Spectrometry

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

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