Poly(vinyl acetate) and Poly(vinyl propionate) Star Polymers via Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization

2005 ◽  
Vol 53 (4) ◽  
pp. 231-242 ◽  
Author(s):  
Daniel Boschmann ◽  
Philipp Vana
Keyword(s):  
Vinyl Acetate ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Star Polymers ◽  
Reversible Addition ◽  
Vinyl Propionate

Doubly-responsive hyperbranched polymers and core-crosslinked star polymers with tunable reversibility

2015 ◽  
Vol 6 (45) ◽  
pp. 7871-7880 ◽  
Author(s):  
Sunirmal Pal ◽  
Megan R. Hill ◽  
Brent S. Sumerlin
Keyword(s):  
Chain Transfer ◽  
Raft Polymerization ◽  
Star Polymers ◽  
Hyperbranched Polymers ◽  
Reversible Addition ◽  
Redox Responsive

Thermo- and redox-responsive hyperbranched copolymers were prepared by statistical copolymerization of N-isopropylacrylamide (NIPAM) and N,N′-bis(acryloyl)cystamine (BAC) by reversible addition–fragmentation chain transfer (RAFT) polymerization.

Synthesis of functionalized poly(vinyl acetate) mediated by alkyne-terminated RAFT agents

RSC Advances ◽  
2015 ◽  
Vol 5 (111) ◽  
pp. 91225-91234 ◽  
Author(s):  
Joana. R. Góis ◽  
Anatoliy V. Popov ◽  
Tamaz Guliashvili ◽  
Arménio C. Serra ◽  
Jorge F. J. Coelho
Keyword(s):  
Vinyl Acetate ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Reversible Addition

Two new xanthates with alkyne functionalities were synthesized for the reversible addition fragmentation chain transfer (RAFT) polymerization of vinyl acetate (VAc).

RAFT Polymerization of Monomers with Highly Disparate Reactivities: Use of a Single RAFT Agent and the Synthesis of Poly(styrene-block-vinyl acetate)

2013 ◽  
Vol 66 (12) ◽  
pp. 1564 ◽  
Author(s):  
Lily A. Dayter ◽  
Kate A. Murphy ◽  
Devon A. Shipp
Keyword(s):  
Block Copolymers ◽  
Vinyl Acetate ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Good Control ◽  
Scanning Calorimetry ◽  
Styrene Polymerization ◽  
Reversible Addition ◽  
Raft Agent ◽  
End Group

A single reversible addition–fragmentation chain transfer (RAFT) agent, malonate N,N-diphenyldithiocarbamate (MDP-DTC) is shown to successfully mediate the polymerization of several monomers with greatly differing reactivities in radical/RAFT polymerizations, including both vinyl acetate and styrene. The chain transfer constants (Ctr) for MDP-DTC for both these monomers were evaluated; these were found to be ~2.7 in styrene and ~26 in vinyl acetate, indicating moderate control over styrene polymerization and good control of vinyl acetate polymerization. In particular, the MDP-DTC RAFT agent allowed for the synthesis of block copolymers of these two monomers without the need for protonation/deprotonation switching, as has been previously developed with N-(4-pyridinyl)-N-methyldithiocarbamate RAFT agents, or other end-group transformations. The thermal properties of the block copolymers were studied using differential scanning calorimetry, and those with sufficiently high molecular weight and styrene composition appear to undergo phase separation. Thus, MDP-DTC may be useful for the production of other block copolymers consisting of monomers with highly dissimilar reactivities.

Copolymerization of N-Vinylcarbazole and Vinyl Acetate via Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization

2008 ◽  
Vol 261 (1) ◽  
pp. 46-53 ◽  
Author(s):  
Jian Zhu ◽  
Xiulin Zhu ◽  
Zhenping Cheng ◽  
Zhengbiao Zhang
Keyword(s):  
Vinyl Acetate ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Reversible Addition

scholarly journals Living Radical Polymerization by the RAFT Process

2005 ◽  
Vol 58 (6) ◽  
pp. 379 ◽  
Author(s):  
Graeme Moad ◽  
Ezio Rizzardo ◽  
San H. Thang
Keyword(s):  
Radical Polymerization ◽  
Polymer Brushes ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Star Polymers ◽  
Living Radical Polymerization ◽  
Factors Influencing ◽  
Reversible Addition ◽  
Complex Architectures

This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC(=S)SR] by a mechanism of reversible addition–fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.

Dendrimers as Scaffolds for Reversible Addition Fragmentation Chain Transfer (RAFT) Agents: a Route to Star-Shaped Block Copolymers

2005 ◽  
Vol 58 (6) ◽  
pp. 483 ◽  
Author(s):  
Xiaojuan Hao ◽  
Eva Malmström ◽  
Thomas P. Davis ◽  
Martina H. Stenzel ◽  
Christopher Barner-Kowollik
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Butyl Acrylate ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Star Polymers ◽  
Size Exclusion ◽  
Chain Extension ◽  
Reversible Addition ◽  
Star Block Copolymers

Star-shaped block copolymers of styrene and n-butyl acrylate having three, six, and twelve pendent arms were successfully synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization. Dendritic cores (based on 1,1,1-trimethylolpropane) of generation 0, 1, and 2 have been functionalized with 3-benzylsulfanylthiocarbonylsulfanylpropionic ester groups and have subsequently been employed to mediate the polymerization of styrene and n-butyl acrylate to generate macro-star-RAFT agents as starting materials for chain extension. The chain extension of the macro-star-RAFT agents with either styrene or n-butyl acrylate by bulk free radical polymerization at 60°C gives narrowly distributed polymer (final polydispersities close to 1.2) increasing linearly in molecular weight with increasing monomer-to-polymer conversion. However, with an increasing number of arms (i.e., when going from three- to twelve-armed star polymers), the chain extension becomes significantly less efficient. The molecular weight of the generated block copolymers was assessed using 1H NMR spectroscopy as well as size exclusion chromatography calibrated with linear polystyrene standards. The hydrodynamic radius, Rh, of the star block copolymers as well as the precursor star polymers was determined in tetrahydrofuran by dynamic light scattering (90°) at 25°C. Interestingly, the observed Rh–Mn relationships indicate a stronger dependence of Rh on Mn for poly(butyl acrylate) stars than for the corresponding styrene polymers. Rh increases significantly when the macro-star-RAFT agent is chain extended with either styrene or n-butyl acrylate.

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