Synthesis of polymers bearing monothio-orthoester groups using a direct route from dithioester-containing monomers and polymers

Hadjout, Slimane; Lévesque, Guy; Pham, Thi‐Nhàn; Trân, Huu-Nhân

doi:10.1016/s0032-3861(96)00933-0

Cited by 4 publications

(2 citation statements)

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“…More recently, a dithioate ester was used as a transfer agent aimed at preventing the gelation of a radical polymerization containing a difunctional monomer . Alternatively, the dithioate ester chain ends can be further modified to provide the target functionality …”

Section: Introductionmentioning

confidence: 99%

“…14 Alternatively, the dithioate ester chain ends can be further modified to provide the target functionality. 15 In the work reported here we describe the use of an imidazole functional RAFT agent, 1, used to prepare stimuli responsive poly(N-isopropylacrylamide) (PNIPAM), highly, branched polymers with imidazole groups at the chain ends. The latter function finds application as a ligand in protein purification [16][17][18][19][20] and potentially in gene and drug delivery.…”

Section: Introductionmentioning

confidence: 99%

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Highly Branched Poly(N-isopropylacrylamide)s with Imidazole End Groups Prepared by Radical Polymerization in the Presence of a Styryl Monomer Containing a Dithioester Group

2005

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Highly branched poly(N-isopropylacrylamide) (PNIPAM) compounds were prepared by copolymerization of 3H-imidazole-4-carbodithioic acid 4-vinylbenzyl ester, 1, with N-isopropylacrylamide (NIPAM) using reversible addition−fragmentation chain transfer (RAFT) polymerization. The polymerizations proceeded well with few side reactions. An increase in the content of 1 in the monomer feed appears to increase the number of branch chains, and at the same time no evidence was obtained for the presence of substituted acrylamide chain ends that may potentially result via elimination of the dithioate group. The polymer products show a clear tendency to increased molecular weight as the extent of conversion of monomer increases, while size exclusion chromatography (SEC) profiles indicate a complex distribution of molecular weights compared to linear polymers obtained with a non-RAFT carboxylate monomer. Both NMR and viscometry indicate that, as expected, increasing the amount of 1 in the feed has the effect of increasing the degree of branching in the final product. This increase in branching reduces the intrinsic viscosity of the solutions of the highly branched polymers compared to similar linear polymers. Poly(N-isopropylacrylamide) displays a lower critical solution temperature (LCST) in aqueous solutions, and cloud point data indicate a clear effect of chain architecture on the temperature at which this transition occurs. Thus, a set of linear analogous copolymers have LCST's that, for equivalent mole fractions of imidazole content, are higher than the similar highly branched polymers. However, on complexation of copper by the imidazole groups the LCSTs of the linear and highly branched sets cannot be differentiated.

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Section: Introductionmentioning

confidence: 99%