Regioselective Esterification and Etherification of Cellulose: A Review

Abstract

Deep understanding of the structure-property relationships of polysaccharide derivatives depends on the ability to control the position of the substituents around the monosaccharide ring and along the chain. Equally important is the ability to analyze position of substitution. Historically, both synthetic control and analysis of regiochemistry have been very difficult for cellulose derivatives, as for most other polysaccharide derivatives. With the advent of cellulose solvents that are suitable for chemical transformations, it has become possible to carry out cellulose derivatization under conditions sufficiently mild to permit increasingly complete regiochemical control, particularly with regard to the position of the substituents around the anhydroglucose ring. In addition, new techniques for forming cellulose and its derivatives from monomers, either by enzyme-catalyzed processes or chemical polymerization, permit us to address new frontiers in regiochemical control. We review these exciting developments in regiocontrolled synthesis of cellulose derivatives and their implications for in-depth structure-property studies.

Reactive extrusion of bio-based polymer blends and composites – Current trends and future developments

“…First of them is related to the modification of the polymer matrix [55,56], while second is focused on size reduction [57], treatment or functionalization of cellulosic filler/fiber. In this subchapter we will focus on the second route related to the surface of filler/fiber, which can be successfully modified by silane treatment [58,59], mercerization [60,61], acetylation [62,63] maleic anhydride treatment [64], esterification and etherification [65,66], isocyanate [67], potassium permanganate [68] and other chemical treatment methods [69][70][71]. Furthermore, different kinds of surfactants and plasticizers applied as physical additives were considered as wetting agents to reduce the tensions in boundary between polymer matrix and reinforcement phase [72][73][74].…”

Cellulose Oxidation and the Use of Carboxyl Cellulose Metal Complexes in Heterogeneous Catalytic Systems to Promote Suzuki-Miyaura Coupling and C−O Bond Formation Reaction

“…Commercial microcrystalline cellulose from Merck (Art.2331), n-oxil-2,2,6,6-tetramethylpiperidine (TEMPO), sodium bromide, a 12% sodium hypochlorite solution, bromobenzene, bromoanisole, arylboronic acids, potassium carbonate (K 2 CO 3 ), palladium acetate (II) (Pd(OAc) 2 ), nickel acetate (II) (Ni(OAc) 2 ), copper acetate (II) (Cu(OAc) 2 ) and other solvents and reagents were analytical grade and used as purchased from commercial sources, without further purification.…”

“…The metal carboxyl cellulose (MCC) catalysts were prepared by treating 1 mmol of corresponding metal acetate (Pd(OAc) 2 , Ni(OAc) 2 and Cu(OAc) 2 ) with 4 mmol of the NaCC in a mixture of methanol/acetonitrile 1:1 (4 mL). The mixture was kept under stirring for 2 h at 60 °C.…”

“…Indeed, some derivatives have been developed and are actually manufactured on an industrial scale and applied in coatings, laminates, optical films, building materials, pharmaceuticals, foodstuffs and cosmetics. 2 On the other hand, the main challenge of modern catalysis is to achieve environment-friendly processes, using sustainable resources and very active catalysts. [3][4][5][6] In this regard, biopolymers are attractive for use combined with transition metal catalysts for further applications in organic synthesis, fine chemical and flow reactors, [7][8][9][10][11][12][13][14] and cellulose may have a great potential of use in heterogeneous catalysis.…”

Extraction of Wheat Straw with Aqueous Tetra-n-Butylphosphonium Hydroxide

“…In a biorefinery concept, paper-related products are not the sole area of interest. Lower quality fibres can be used for various applications in which fibre properties may not be essential, e.g., enzymatic hydrolysis en route to biofuels (Brown and Brown 2013;Qureshi et al 2013), cellulose derivatisation (Sirviö et al 2011;Fox et al 2011;Cunha and Gandini 2010), or to other value-added products.…”