Toward industrial grafting of cellulosic substrates via ARGET ATRP

Abstract

For the past decade, the interest in controlled grafting of cellulose has increased immensely. Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) has attracted the most interest; however, the sensitivity of this system has so far hindered its utilization in industry. In this study, filter paper, dissolving pulp, bleached and unbleached Kraft-pulp, and chemi-thermomechanical pulp papers were grafted with methyl methacrylate, employing activators regenerated by electron transfer (ARGET) ATRP. The reactions were performed in bulk or with small amounts of aqueous solutions, with no deoxygenation performed. To further demonstrate the robustness of this method towards simpler and more industry-friendly processes, the polymerizations were conducted in glass jars with screw lids. The possibility of recycling the reaction solution was also explored. We believe his thorough study to be an important step towards industrializing the "grafting-from" concept, and the results herein can most likely be extended to other surfaces and monomers.

Polymer-grafted modification of cotton fabrics by SI-ARGET ATRP

“…These drawbacks can be overcome by an improved ATRP technique, activators regenerated by electron transfer for ATRP (ARGET ATRP) process, which has been developed by Matyjaszewski's group more recently and greatly reduced sensitivity to oxygen by the introduction of an excess of reducing agent in the reaction [42,43]. Surface modification of solid cellulose and related materials, such as filter paper, cellulose membranes and wood, has been already investigated by several researchers [44][45][46][47], but information concerning grafted cotton fabric is rather scarce in the literature [48].…”

Cellulose-based graft copolymers prepared by simplified electrochemically mediated ATRP

“…A variety of approaches has been reported for the modification of cellulose by graft polymerization, provides a significant route that combines the advantages of using natural cellulose and synthetic macromolecules in a wide range of potential applications, such as new materials for drug delivery devices, coatings, sorption agents, and membranes [2,3,8]. One of them is the 'grafting-from' technique, which uses a multi-functional initiator to initiate atom transfer radical polymerization (ATRP) [9][10][11]. Numerous monomers have been grafted from cellulose via ATRP, such as methyl methacrylate [2,3,11,12], N,N-dimethylamino-2-ethyl methacrylate [5,13], di(ethylene glycol) ethyl ether acrylate [12], styrene [2], N-isopropylacrylamide [14,15], and 2-methacryloyloxyethyl phosphorylcholine [10], but synthesis of cellulose-graft-(poly(acrylic acid)-blockpoly(oligo(ethylene glycol) acrylate) (Cell-g-(PAAb-POEGA) has not yet been reported.…”

“…One of them is the 'grafting-from' technique, which uses a multi-functional initiator to initiate atom transfer radical polymerization (ATRP) [9][10][11]. Numerous monomers have been grafted from cellulose via ATRP, such as methyl methacrylate [2,3,11,12], N,N-dimethylamino-2-ethyl methacrylate [5,13], di(ethylene glycol) ethyl ether acrylate [12], styrene [2], N-isopropylacrylamide [14,15], and 2-methacryloyloxyethyl phosphorylcholine [10], but synthesis of cellulose-graft-(poly(acrylic acid)-blockpoly(oligo(ethylene glycol) acrylate) (Cell-g-(PAAb-POEGA) has not yet been reported. It is expected that these synthesized graft copolymers have great potential in biomedical, such as tissue engineering scaffolds with double-responsive and antifouling properties.…”

Poly(methyl methacrylate)‐grafted cellulose nanocrystals: One‐step synthesis, nanocomposite preparation, and characterization

“…Habibi et al were the first to report “grafting from” CNCs using caprolactone and a ring‐opening polymerization technique . Since then, controlled polymerization methods such as atom transfer radical polymerization (ATRP) have been extended from working with cellulose filter paper to CNCs . ATRP from the surface of filter paper, wood, or pulp fibres is relatively straightforward, since the pre‐polymerization step to attach the initiator can easily be done (and purified) in various solvents.…”

“…Since then, controlled polymerization methods such as atom transfer radical polymerization (ATRP) have been extended from working with cellulose filter paper to CNCs . ATRP from the surface of filter paper, wood, or pulp fibres is relatively straightforward, since the pre‐polymerization step to attach the initiator can easily be done (and purified) in various solvents. However, when modifying CNCs with ATRP, initiator attachment involves lengthy solvent exchange steps and destabilization of CNC dispersions .…”