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[Home](https://www.sigmaaldrich.com/US/en)[Polymer Synthesis Techniques](https://www.sigmaaldrich.com/US/en/applications/materials-science-and-engineering/polymer-synthesis)Evaluation of RAFT Agents
# Evaluation of RAFT Agents
__Jeremy Bartels, Sebastian Grajales, Kaushik Patel, Kanth V. B. Josyula, Gangadhar Panambur and Scott Batcheller__
## RAFT polymerization process
In 1998, members of an Australian Commonwealth Scientific and Research Organization (CSIRO) team discovered the RAFT polymerization method.1

## Why use RAFT methods?
- The process allows radical-initiated growing polymer chains to degeneratively transfer reactivity from one to another through the use of key functional groups (dithioesters, trithiocarbonates, xanthates and dithiocarbamates).
- RAFT agents help to minimize out-of-control growth and prevent unwanted termination events from occurring, effectively controlling polymer properties like molecular weight and polydispersity.
- RAFT agents are commercially available.
- RAFT does not use any cytotoxic heavy metal components (unlike ATRP).
## Classes of RAFT agents
- __Dithiocarbamates__  Z1 is typically -Me or other alkyl
Z2 is typically -Ph or other aromatic
- __Xanthates__  Z is typically an alkyl chain (Et)
- __Dithioesters__  Z can vary widely, but is typically -Ph
- __Trithiocarbonates__  Z is typically an alkyl group (C12H25, etc.)
## Versatility of RAFT
- RAFT is compatible with most functional groups and solvents, including water.
- RAFT polymerizations are often mildly tolerant to oxygen content, especially when compared to living anionic polymerizations.
- RAFT agents may be tuned to give polymers with telechelic functionality, for further processing/ binding events.
- The RAFT technique requires no special equipment or vacuum glassware.
- RAFT polymers can be applied to any field, from electronics to cell biology.
## Compatibility table

## RAFT efficacy
A series of five RAFT polymerizations were carried out using our RAFT agents, monomers, and initiators:
| | | | | | | |
|-------------------|-----------|-------------|------------|------------|------------|------|
| Polymer | Conv (%); | MnTheo (Da) | MnNMR (Da) | MwGPC (Da) | MnGPC (Da) | PDI |
| 1\. P*t*BA | 33% | 4,600 | 4,800 | 5,000 | 4,700 | 1.06 |
| 2\. P*t*BA-*b*-PS | 35% | 7,400 | 7,200 | 7,200 | 6,300 | 1.15 |
| 3\. PEO-*b*-PS | 29% | 7,300 | 7,400 | 7,000 | 6,300 | 1.04 |
| 4\. PVAc | 65% | 12,300 | 12,300 | 18,000 | 14,800 | 1.21 |
| 5\. PMMA | 60% | 15,400 | 15,000 | 16,400 | 14,900 | 1.10 |
### New class of RAFT CTAs: Universal, pH-switchable RAFT agents

## Materials
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### References
1\.
Chiefari J, Chong YK(, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, et al. 1998. Living Free-Radical Polymerization by Reversible Addition?Fragmentation Chain Transfer: The RAFT Process. Macromolecules. 31(16):5559-5562. [https://doi.org/10.1021/ma9804951](https://doi.org/10.1021/ma9804951)
## Acknowledgements
- Shashi Jasty, Ph.D.
- John Radke
- Ilya Koltover, Ph.D.
- Angel Thompson
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