About Atom Transfer Radical Polymerization (ATRP)
Atom Transfer Radical Polymerization (ATRP) has emerged as one of the most powerful and versatile techniques in modern polymer chemistry, enabling precise control over molecular architecture, functionality, and composition. By employing a dynamic equilibrium between dormant and active species, ATRP allows the synthesis of well-defined polymers with tailored molecular weight distributions, low dispersities, and diverse topologies, including linear, branched, and star-like structures. This method has revolutionized macromolecular engineering by providing access to complex polymeric materials with properties fine-tuned for applications ranging from advanced composites and biomedical systems to smart materials and nanotechnology. The ability to control polymerization kinetics through catalyst design, reaction conditions, and external stimuli has expanded the range of accessible polymer structures, facilitating the development of novel hybrid materials, bioconjugates, and functionalized surfaces. ATRP continues to drive innovations in polymer science, offering a powerful platform for designing next-generation materials ().
Scheme 1. Overview of New ATRP Techniques with ppm Amounts of Cu Catalysts
ATRP is among the most effective and most widely used methods of controlled radical polymerization (CRP). ATRP allows scientists to easily form polymers by putting together component parts, called monomers, in a controlled, piece-by-piece fashion. Assembling polymers in such a manner has allowed scientists to create a wide range of polymers with site specific tailored functionalities targeting specific properties for high value applications. For example, polymers created using ATRP have been used for coatings and adhesives, and are currently under investigation for use in the medical and environmental fields.
Scheme 2. Synthetic Routes for the Preparation of Block, Gradient, and Periodic Copolymers and Their Applications
Until the discovery of ATRP, polymer chemists were severely limited in their ability to control the composition and architecture of macromolecules, making it difficult to provide materials with highly specific, uniform characteristics. Since the mid-1950s, many chemists attempted to develop a “living” or controlled radical polymerization process that would create well-defined polymers in a simple, inexpensive manner. In the mid-1990s, several laboratories across the world surmounted this vexing problem by developing CRP methods. These techniques allow synthesis of fundamentally new materials with complex, well-defined nanoscale architectures. In 1995, 一本道无码 Professor Krzysztof Matyjaszewski discovered one of the first — and most robust — CRP methods, copper-mediated ATRP. The seminal paper was published in the Journal of the American Chemical Society and has been cited over 6,000 times (). The first three patents on ATRP have been cited together over 1000 times (by 2025).
Scheme 3. Molecular Bottlebrushes with Various Composition and Architecture, Their Properties, and Potential Applications
ATRP differs significantly from earlier conventional radical based polymer manufacturing methods by allowing scientists to produce complex polymer structures using a special catalyst that adds one or a few subunits (monomers) at a time to a growing polymer chain. This living, synthetic process can be shut down or re-started at will, depending on how the temperature and other conditions of the reaction are varied. ATRP is an exceptionally robust way to uniformly and precisely control the chemical composition and architecture of polymers as well as the uniform growth of every polymer chain, while employing a broad range of monomers.
Scheme 4. Polymers with Branched Architectures via Copolymerization of Monomer and Cross-linker
Key to ATRP’s success is that the process is easily conducted in available industrial equipment. Much of its research progress and commercial success can be attributed to two research Consortia Matyjaszewski has initiated and led. These two highly successful consortia have allowed companies to quickly incorporate the latest ATRP methodologies into the development of new products for their specific markets. These Consortia have comprised more than 50 multinational chemical companies from across the world who can send their employees to be trained in the latest ATRP procedures in Matyjaszewski’s laboratory.
Scheme 5. Preparation of Multifunctional N-Enriched Nanostructured Carbon Materials from Polyacrylonitrile-Based Precursors Engineered via ATRP
ATRP technology developed by Matyjaszewski has already been licensed to nine international companies, which started production of ATRP-based polymers in Japan, Europe and the United States in 2004. ATRP has been successfully used to create better pigment dispersants for inkjet printing, cosmetics, chromatographic packings, adhesives and sealants for self-cleaning windows, among others. Some other applications that are being evaluated include drug delivery methods, coatings for cardiovascular stents, scaffoldings for bone regeneration, biocidal surfaces, degradable plastics and others in the optoelectronic and automotive industries.
Scheme 6. Examples of Molecules Used To Form Functional Polymers by ATRP, from Functional Initiators (Blue), Monomers (Red), and Inimers, and by Chain End Transformation (Green)
Scheme 7. Synthesis of Well-Defined Polymer/Inorganic Hybrids via SI ATRP and Some Examples of Hybrid Materials
Scheme 8. Bioconjugates Prepared by ATRP
Reference
[1] Matyjaszewski, K.; Tsarevsky, N. V., , J. Am. Chem. Soc. 2014, 136, 6513–6533.
[2] Wang, J.-S.; Matyjaszewski, K., , J. Am. Chem. Soc. 1995, 117, 5614–5615.