Single‐electron transfer‐living radical copolymerization of butyl methacrylate and divinylbenzene for preparation of oil‐absorbing gel

Abstract

Crosslinking copolymerization of butyl methacrylate with a small amount of divinylbenzene (DVB) was carried out using single‐electron transfer‐living radical polymerization initiated with carbon tetrachloride (CCl4) and catalyzed by Cu(0)/N‐ligand in N,N‐dimethylformamide to produce a highly oil‐absorbing gel. The polymerization, gelation process, and oil‐absorbing properties were studied in detail. Analysis of monomer conversion with reaction time showed that the polymerization followed first‐order kinetics for both linear and crosslinking polymerization before gelation. Higher levels of DVB led to earlier gelation and the influence of N‐ligand on gelation was also significant. Under optimal conditions, oil absorption of the prepared gel to chloroform could reach 42.1 g·g−1. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3233–3239

Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis

“…Moreover, although polymerization of methacrylic acid is not possible via SET-LRP, copolymerization with MMA can be achieved (Đ ∼ 1.3) . Oligo­(ethylene oxide) methyl ether methacrylate (OEGMA), − di­(ethylene glycol)­methyl ether methacrylate (DEGMEMA), tri­(ethylene glycol)­methyl ether methacrylate (TEGMEMA), 2-hydroxyethyl methacrylate (HEMA), butyl methacrylate (BMA), − tert -butyl methacrylate ( t BMA), , ethyl methacrylate (EMA), isobornyl methacrylate (IBMA), N , N -dimethyl- N -methacryloyloxyethyl- N -sulfobutyl ammonium (DMBS), 1′-(2-methacryloxyethyl)-3′,3′-dimethyl-6-nitrospiro-(2 H -1-benzopyran-2,2′-indoline) (SPMA), and 2-( tert -butyl-aminoethyl) methacrylate (TBAEMA) have also been evaluated via SET-LRP protocol showing a good level of control in all cases. More functional monomers have also been polymerized, including γ-butyrolactone methacrylate (GBLMA), methyl adamantyl methacrylate (MAMA), 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPMA), and 1 H ,1 H ,5 H -octafluoropentyl methacrylate (OFPMA) (Figure and Table ).…”

“…Interestingly, CHCl 3 and CHBr 3 are monofunctional initiators while CHI 3 behaves as a monofunctional initiator at low conversion but transitions to a bifunctional one at high conversion. Finally, alkyl halide initiators (e.g., carbon tetrachloride (CCl 4 ), ,,,, for the polymerization of methacrylates and acrylonitrile), sulfonyl halide initiators ( p -toluene sulfonyl chloride (TsCl) ,,,, suitable for both methacrylates and acrylates), amide initiators (2-chloropropionamide (CPA), 2-bromo-2- N -phenyl-propionamide (BrPPA) can be applied when acrylates, methacrylates, and acrylamides are targeted), and nitrile initiators (e.g., 2-bromopropionitrile (BPN) for acrylates) have demonstrated to be effective initiators for SET-LRP. A variety of functional initiators have also been employed including phosphonate bearing initiators (PBI), , an arsenic iniatiator (AsI), a dithiophenol maleimide initiator (DtMI), and a propargyl 2-bromoisobutyrate initiator (PBIB) (Figure ).…”

“…Interestingly, although Tren provided a slower polymerization rate when compared with Me 6 -Tren, the high end-group functionality was maintained demonstrating that the commercially available Tren is also an efficient ligand . 1,1,4,7,10,10-Hexamethyltriethylenetetramine (HMTETA), ,, 2,2′-bipyridine (Bipy), , and 4,4′-dinonyl-2,2′-bipyridine (diNbpy) have also been employed, although the disproportionation in the presence of the latter two is negligible and, thus, a mixture of Cu(0) and Cu­(I) activation must occur. On the contrary, Me 6 -Tren, Tren, and PMDETA can preferentially form stronger complexes with Cu II Br 2 rather than with Cu I Br and thus accelerate the disproportionation of Cu I Br into Cu(0) and Cu II Br 2 (Figure ).…”

“…In a subsequent paper of the same group, a novel high oil-absorbing cross-linked gel was synthesized utilizing the aforementioned monomers resulting in homogeneous polymer networks . More recently, Fu and co-workers studied the cross-linking copolymerization of BMA with a small amount of divinylbenzene (DVB) via SET-LRP to produce a highly oil-absorbing gel . Therefore, SET-LRP enabled for the first time the synthesis of novel homogeneous polymer structures preserving functional ends and resulting in materials with enhanced oil absorbency.…”

Preparation and evaluation of a polymeric gel containing ionic liquid-functionalized MWCNTs as a novel class of organic solvent absorbent

“…Polymeric gels are crosslinked polymers that can absorb large amount of polar or non‐polar solvents depending on their chemical structure, that is, hydrophobic polymeric gels absorb organic solvents and oils while hydrophilic polymeric gels have very high water absorption properties. A great number of organic solvent and oil absorbent polymeric gels have been reported in literature . However, new organic solvent absorbents with high absorption capacity, low water pickup and reusability are still required.…”