Synthesis of sequence controlled acrylate oligomers <i>via</i> consecutive RAFT monomer additions

Vandenbergh, Joke; Reekmans, Gunter; Adriaensens, Peter; Junkers, Thomas

doi:10.1039/c3cc45994b

Cited by 109 publications

(77 citation statements)

References 28 publications

(22 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Though its applicability to the synthesis of higher molecular weight sequence controlled polymers is yet to be proven, Moad and coworkers (70) and, more recently, Junkers and coworkers presented the preparation of sequence controlled dimers and tetramers respectively by stepwise single-monomer addition in a RAFT process (71). The procedure by Junkers and coworkers relied on the addition of a single monomer (on average) to the CTA by using 10 equivalents of a monomer to the CTA in the presence of a small amount of AIBN and heating the solution for a short time.…”

Section: Figurementioning

confidence: 98%

Simultaneous Control over Monomer Sequence and Molecular Weight Using the RAFT Process

Brummelhuis

Weck

2015

ACS Symposium Series

View full text Add to dashboard Cite

A simultaneous control over molecular weight and monomer sequence is highly desirable since they strongly influence the properties of polymers.The reversible additionfragmentation chain-transfer (RAFT) process is ideally suited to provide control over molecular weight for a wide range of copolymerizations because of the tolerance of the RAFT process towards functional groups and reaction conditions. Here we highlight that RAFT can be used to prepare polymers with well-defined alternating or periodic monomer sequences and controlled, narrowly distributed, molecular weight.

show abstract

Section: Figurementioning

confidence: 98%

Simultaneous Control over Monomer Sequence and Molecular Weight Using the RAFT Process

Brummelhuis

Weck

2015

ACS Symposium Series

View full text Add to dashboard Cite

show abstract

“…Moad and coworkers [72] synthesized macro-RAFT agents containing styrene-N-isopropylacrylamide (NIPAM) co-dimer. Junkers and coworkers [73] reported macro-RAFT agents containing four units of acrylates with different side groups. In these syntheses, the molar ratio of the original RAFT agents to the monomer was kept as 1:1.…”

Section: Single Monomer Additionmentioning

confidence: 99%

Recent developments in the synthesis of sequence controlled polymers

2015

Sci. China Chem.

View full text Add to dashboard Cite

“…15,16 The on-line microreactor procedure towards screening SUMI-2AB has been described previously. 15,16 The on-line microreactor procedure towards screening SUMI-2AB has been described previously.…”

Section: Synthesismentioning

confidence: 99%

“…18,19 In this way, up to two monomer units could be efficiently inserted into the C-S bond of a RAFT agent. 15 With the help of recycling preparative size exclusion chromatography, isolation of SUMI oligomers with up to 4 monomer units and thus (including the RAFT-typical groups) 6 functionalities in precise order was demonstrated (see Scheme 1 for a general reaction scheme). In a similar approach, we demonstrated that one can perform SUMIs using only acrylates (and thus with monomers of a very similar reactivity) by accepting the statistical nature of the reactions, but performing advanced product separation, in which the desired SUMI products are isolated from their by-products (species in which either no monomer or several monomers were built in).…”

Section: Introductionmentioning

confidence: 99%

Efficiency assessment of single unit monomer insertion reactions for monomer sequence control: kinetic simulations and experimental observations

et al. 2015

Self Cite

View full text Add to dashboard Cite

The reaction efficiency of single unit monomer insertion (SUMI) reactions via the reversible addition fragmentation chain transfer (RAFT) method is investigated in detail by the determination of obtained product yields of optimized batch and microflow synthesis procedures in combination with kinetic simulations of the radical insertion process. A method is developed to obtain exact concentration information on different SUMI products from calibration of the corresponding electrospray ionization mass spectra that are recorded on-line during synthesis. Experimental data show that isolated yields decrease for each subsequent SUMI reaction. This effect is investigated via kinetic modelling to understand which parameters have a beneficial or negative influence on the reaction outcome. Although most reaction conditions (such as monomer concentration or radical flux) do not play a considerable role in the obtainable yield of the insertion reaction, the model clearly shows that the propagation rate coefficient must display a strong chain-length dependency in order to explain the experimental observations. When taken into account, the simulations very well fit the experimental data obtained from optimized microreactor flow synthesis and recommendations for SUMI reactions are formulated. Finally, the optimized SUMI conditions obtained from microreactor experiments and kinetic modelling insights have been applied to upscale the SUMI synthesis reactions in a mesoflow reactor. This demonstrates the simple upscalability of continuous flow reactions and opens the pathway towards future synthesis of longer sequence controlled oligomers. † Electronic supplementary information (ESI) available: Details of the experimental setups, ESI-MS calibration information and complementary experimental data. See Scheme 2 Synthetic pathway towards sequence controlled SUMI-1A, SUMI-2AB and SUMI-3ABC using radical monomer insertion via RAFT polymerization. Polymer Chemistry PaperThis journal is

show abstract

Synthesis of sequence controlled acrylate oligomers via consecutive RAFT monomer additions

Cited by 109 publications

References 28 publications

Simultaneous Control over Monomer Sequence and Molecular Weight Using the RAFT Process

Simultaneous Control over Monomer Sequence and Molecular Weight Using the RAFT Process

Recent developments in the synthesis of sequence controlled polymers

Efficiency assessment of single unit monomer insertion reactions for monomer sequence control: kinetic simulations and experimental observations

Contact Info

Product

Resources

About