BonLab does PISA with RAFT-agent version 0.1

Call them plastics, polymers, elastomers, thermoplasts, thermosets, or macromolecules. What’s in the name? Despite the current negative press in view of considerable environmental concerns on how we deal with polymer materials post-use, it cannot be denied that polymers have been a catalyst in the evolution of human society in the 20st century, and continue to do so.

One of the synthetic pathways toward polymer molecules is free radical polymerization, a process known since the late 1800s and conceptually developed from the 1920s-1930s onwards. Since the 1980s it gradually became possible to tailor the chemical composition and chain architecture of a macromolecule. The process is called reversible deactivation radical polymerization (RDRP), also known as controlled or living radical polymerization. By grabbing control on how individual polymer chains are made, with the ability to control the sequencing of its building blocks, known as monomers, true man-made design of large functional molecules has become reality. This architectural control of polymer molecules allows for materials to be formulated with unprecedented physical and mechanical properties.

One interesting phenomenon is that when we carry out an RDRP reaction using a “living” polymer (a first block) dissolved in for example water and try to extend the macromolecule by growing a second block that does not dissolve in water, it is possible to arrange the blockcopolymer molecules by grouping them together into a variety of small (colloidal) structures dispersed in water. More interestingly, these assembled suprastructures have the ability to dynamically change shape throughout the polymerization process, for example to transform from spherical, to cylindrical, to vesicle type objects. This Polymerization Induced Self-Assembly process has been given the acronym PISA.

One way to carry out the synthesis of macromolecules by reversible deactivation radical polymerization is to make use of the concept of Reversible Addition-Fragmentation chain-Transfer, known as RAFT. This polymerization process has conventionally now uses sulfur-chemistry in the synthesis of RAFT-agents (versions 1.0 and up so to say), which efficiently controlled the growth of macromolecules. It is based on an invention from the mid 1990s, but more interestingly came to fruition by the realization that methacrylate-based macromonomers acted as RAFT-agents (here version 0.1). These latter compounds were, however, not very efficient, and abandoned.

We now show in the BonLab’s latest paper published in ACS Macro Letters that methacrylate-based macromonomers can be used successfully as RAFT-agents in Polymerization Induced Self-Assembly (PISA) processes by carefully considering the mechanistic aspects.

ML2017BonLab Stefan Bon says: “Our team is delighted with the results and we are happy the paper features in ACS Macro Letters. RAFT-ing the classic way will for sure get more than a 2nd try! To show that PISA with version 0.1 RAFT-agents is indeed possible, was an excellent team effort by PhD researcher Andrea Lotierzo, and 2nd year undergraduate Warwick Chemistry student (now 3rd year) Ryan Schofield.”

The use of this class of "primitive" RAFT-agents in heterogeneous polymerizations is however not trivial, because of their inherent low reactivity. In our work we demonstrate that two obstacles need to be overcome, one being control of chain-growth (propagation), the other monomer partitioning. Batch dispersion polymerizations of hydroxypropyl methacrylate in presence of poly(glycerol methacrylate) macromonomers in water showed limited control of chain-growth. Semi-continuous experiments whereby monomer was fed improved results only to some extent. Control of propagation is essential for PISA to allow for dynamic rearrangement of colloidal structures. We tackled the problem of monomer partitioning (caused by uncontrolled particle nucleation) by starting the polymerization with an amphiphilic thermo-responsive diblock copolymer, already “phase-separated” from solution. TEM analysis showed that PISA was successful and that different consecutive particle morphologies were obtained throughout the polymerization process.

The paper can be downloaded from ACS Macro Letters.  DOI: 10.1021/acsmacrolett.7b00857