Grafting studies onto cellulose by atom‐transfer radical polymerization

Abstract

Styrene (Sty), methyl methacrylate (MMA), methacrylamide (MAm) and acrylomorpholine (AcM) were grafted onto powder cellulose by atom-transfer radical polymerization. Cellulose chloroacetate (Cell-ClAc), as a macro-initiator, was first prepared by the reaction of chloroacetyl chloride with primary alcoholic OH groups on powder cellulose. CuBr and 1,2-dipiperidinoethane were used as a transition-metal compound and as a ligand, respectively. These reactions were monitored by FT-IR and weight increase in Cell-ClAc. In case of styrene, although some weight increase occurred, no evidence of grafting could be observed in the FT-IR spectrum, while there were strong evidence of grafting with MMA, MAm and AcM. Cell-graft-MAm, Cell-graft-AcM and Cell-graft-MMA showed new carbonyl bands at 1665, 1640 and 1735 cm −1 , respectively. Dye-uptake and dye-absorption properties of cellulose, for alizarin yellow (basic dye) and bromocresol green (acidic dye), and its moisture-and water-uptake capacities improved with the grafting, but some decrease was observed in thermal stability.

Modification of Cellulose by Using Atom Transfer Radical Polymerization and Ring-Opening Polymerization

“…After stirring and filtration, the residue was purified by methanol, chloroform, and acetone, sequentially. The resultant was dried under vacuum at 40 C to a constant weight. After stirring and filtration, the residue was purified through a sufficient removal of PMMA homopolymer by washing with chloroform and acetone.…”

“…After stirring and filtration, the residual was purified by using THF/ H 2 O (1/10, v/v) three times. The resultant was dried in vacuum at 40 C to a constant weight. Synthesis of Cell-PEMO and Cell-PMMA.…”

“…After stirring and filtration, the residue was purified through a sufficient removal of PMMA homopolymer by washing with chloroform and acetone. And then the purified product was dried under vacuum at 40 C to a constant weight. The operational procedure for preparation of Cell-(PMMAb-PEMO) was similar as Cell-(PEMO-b-PMMA) without the differences of Cell-PMMA as initiator, and EMO as monomer in the ATRP process, and also of that a centrifuge separator was used for the product purification.…”

“…TGA curves of Cellulose, Cell-ClAc, Cell-PEMO, Cell-(PEMO-b-PMMA), Cell-PEMO-PCL, and Cell-(PMMA-b-PEMO) were shown in Figure 5. As well known, cellulose is a material that has not a melting point temperature, and its glass transition temperature appears at 230 C. 38,39 Its thermal degradation starting temperature was 290 C 7,40 approximately, and the degradation course shows a narrow temperature range. However, in the TGA curves of these cellulose derivatives, the degradation starting temperatures exhibited lower values than 290 C of virgin cellulose, and the thermal degradation courses revealed wide temperature ranges.…”

Surface Analysis of Polystyrene-Grafted Keratin Fiber via Surface-Initiated Atom Transfer Radical Polymerization

“…The surface-initiated atom transfer radical polymerization (SI-ATRP) technique has been successfully applied for the surface grafting of polymers from natural biomacromolecules such as cellulose [6][7][8][9], starch [10] and chitosan [11][12][13]. The grafting architectures can be tailored to obtain specific surface properties in a material.…”