Improving the Structural Control of Graft Copolymers. Copolymerization of Poly(dimethylsiloxane) Macromonomer with Methyl Methacrylate Using RAFT Polymerization

Amphiphilic gradient copolymer of [poly(ethylene glycol) methyl ether] methacrylate and styrene via atom transfer radical polymerization

“…(1). [49][50][51] Hence, the reactivity ratio, (r styrene =0.53±0.01) was calculated from the slope by plotting the kinetic data of styrene against those of PEGMA, as shown in Figure 2…”

“…The reactivity of macromonomer was affected by two factors: the effect of diffusion-control associated with the macromonomer at high initial monomer feed ratios, and an incompatibility effect due to the thermodynamic repulsive interactions between the macromonomer and the propagating comonomer chain. 50,51,53 Relatively long poly(ethylene glycol) (PEG) pendant groups in the PEGMA monomer cause a similar macromonomer effect. When PEGMA has high concentration of feed ratio, PEGMA acts as a macromonomer.…”

Experimental Requirements for an Efficient Control of Free‐Radical Polymerizations via the Reversible Addition‐Fragmentation Chain Transfer (RAFT) Process

“…Finally, a difference in the relative comonomer consumption rates between a RAFT and a conventional free radical copolymerization does not necessarily imply a modification of the reactivity ratio values-defined as the ratio between the homo-and the cross-propagation rate coefficients, k aa /k ab and k bb /k ba -since they only depend on [9,13,41,67,68,72,74,80,107,[110][111][112]114,119,121,129,133] a) [135,137,138,140,141] BMA [110,148] a) [140] b) [72,151] EHMA b) [150,151] LMA [133,154] BzMA [107] TFEMA [154] HEMA [157] a) [67,72,110,158] c) [159] NMAS [76] HEMA-TMS [162] TRIS-MA [163] tBDMSMA [164] DMAEMA [67] AEMA [136] GMA c) [171] MMAm …”

“…þþ À À NAM/CMDB [43] þ À À À þ À 10 þþ À þ MMA/PEDB [117] þ À þ À À À MMA/PFADB [113] 11 þþ þ À MA/Dithiobenzoates [252] þ þ À þ þ þ NAM/tBDB [43] 12 þþ þ þ MMA/CDB [114] þ þ þ þ À þ MMA/CPDB [118] A critical parameter of a RAFT polymerization is the radical flux. It can be regulated to optimize the (polymerization duration/MWD control) balance.…”

Nitroxide-mediated controlled/living radical copolymerizations with macromonomers

“…There are numerous examples in the literature of controlled/living radical copolymerizations involving macromonomers employing both ATRP [15][16][17][18][19][20] and RAFT [20][21][22][23]. Controlled/living radical copolymerization results in polymer of vastly different microstructure compared to its conventional radical polymerization counterpart.…”