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The First Dive into the Mechanism and Kinetics of ATRP
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Cite this: Macromolecules 2020, 53, 4, 1115–1118
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https://doi.org/10.1021/acs.macromol.9b02460
Published February 25, 2020

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I have the distinct honor and challenge of writing on the impacts of the work reported in “Controlled/“Living” Radical Polymerization. Halogen Atom Transfer Radical Polymerization Promoted by a Cu(I)/Cu(II) Redox Process”, by Jin-Shan Wang and Krzysztof Matyjaszewski, published in the 28th volume of Macromolecules in 1995. (1,2) On the 75th anniversary of Staudinger’s seminal work whose centennial we are celebrating this year, our understanding of polymer chemistry was taking a leap forward. This paper was a critical milestone in that journey.

By the 1980s, polymer science and the fundamental set of organic chemistries used to make polymer chains for academic interest or industrial use had been well-established and studied for decades. Textbooks described in detail the principal mechanisms and kinetic models of polymer chain growth. Some chemists were exploring new possibilities to control polymerization, but translation of those methods into scalable technologies would require significant effort. Everyone “knew” that while carbon-centered radical-based methods were extremely versatile and provided a rich diversity of copolymers, easily scaled to produce commercial products, they were inherently unstable and uncontrollable species which yielded highly disperse molecular masses (Đ > 2). And yet, in the early 1980s, one of the most exciting races that would turn all of that knowledge on its head saw the first spark of an idea.

At that time, living cationic polymerization was a research topic of interest. One of the seminal discoveries in this field was that highly reactive carbocations could be “tamed” as propagating centers via their reversible activation from covalent species by Lewis acids. Because of this chemical interaction, the lifetime of a propagating chain, before chain transfer or termination, could be extended to permit many propagation cycles and lead to controlled growth of a polymer chain. Such success for controlling the chemistry of carbocation propagating species led researchers in the field to ask whether a similar mechanism could be developed for the yet untamed carbon radical propagating centers.

Carbon-centered radical propagation presented some uniquely appealing features as well as unique challenges. (5) The propagating chain end is inherently less stable and more promiscuous than ionic chain ends. If it could be controlled, however, many more monomers become available for polymerization. A multitude of copolymerizations would become possible—either to form the segments of block copolymers or to be statistically distributed along the chain. The conditions for the reactions also become much less stringent: extreme low temperatures are no longer necessary, and water would not poison the reactions. Only removal of oxygen and other radical inhibitors would become necessary, perhaps mild heating, which is comparatively easy when considering the necessary requirements for ionic polymerizations. These advantages would significantly lower the barriers to researchers using this chemistry in their lab as long as the starting materials were available or not onerous to prepare. They would also open the door to seemingly infinite permutations of copolymers which could target advanced functionality in ways not possible before because the reaction is unaffected by hydroxyls, acids, amides, and many other functional groups.

There were some early efforts to tame carbon radicals for this purpose, (6) though the first fine control as it became used in modern methods came from David Solomon and the outstanding team of scientists at the Commonwealth Scientific and Industrial Research Organization (CSIRO) polymer group in Australia including Ezio Rizzardo and Graeme Moad, who patented their findings on nitroxide mediated radical polymerization. (7−9) By the mid-1990s, at least half a dozen groups were exploring the versatility of this method for reversibly deactivating carbon-centered radical chain ends to prevent the common irreversible side reactions in polymerization. (10) The subtle steric and electronic effects of the nitroxide substituents required organic synthesis skills to tailor the deactivator to the propagating chain end. What was missing to turn this spark into the fire that revolutionized polymer chemistry was a generally accessible method using “off the shelf” ingredients to achieve the same results. This event happened in 1995.

Several communications that year from preeminent polymer chemists, beginning with Sawamoto et al. (12) and quickly followed by Wang and Matyjazewski (13,14) and Percec and Barboiu, (15) had reported the ability of transition metal salts combined with “off the shelf” ligands to control what was hypothesized to be radical polymerization (Figure 1). Each reported system showed a constant concentration of growing radicals, molecular masses determined by the extent of monomer conversion and the initial ratio of monomer to initiator, and consistently low mass dispersities that became lower with higher conversion. The follow-on full paper, submitted on May 2, 1995, delved into the details of the reaction and characterization of the chains produced to focus on the propagation mechanism and eliminate alternatives. It established without a doubt that atom transfer between the chain end and a copper/bipyridyl complex was indeed controlling a radical polymerization process, making the name atom transfer radical polymerization (ATRP) appropriate rather than just catchy.

Figure 1

Figure 1. Participants at a 1995 Symposium at the Romanian Academy in Iasi. Professor Matyjaszewski is fourth from the right, Professor Percec is fifth, and Professor Sawamoto is sixth. All three would publish communications reporting controlled radical polymerization based on transition metal mediated halogen exchange in 1995, leading up to the full paper discussed in this editorial. Reproduced with permission from ref (11). Copyright 2018 Royal Society of Chemistry.

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There were a lot of firsts in this paper. The manuscript was the first appearance of the scheme detailing the catalytic cycling of metal oxidation states with halogen transfer and propagation that would be reproduced in countless forms over the next 25 years. The paper described the first demonstration that polymerizations of four different monomers (styrene, methyl acrylate, butyl acrylate, and methyl methacrylate (MMA)) were all controlled with the same metal–ligand combination and similar conditions. Finally, the manuscript included 13C NMR spectral data matching PMMA tacticity for polymers synthesized by ATRP and conventional radical polymerization (Figure 2). The authors also demonstrated that the ratio of propagation to termination rates (kp/kt) improved with temperature as expected from a radical propagation mechanism.

Figure 2

Figure 2. Reproduction of Figure 6 from ref (1) comparing 13C NMR of PMMA prepared via conventional radical polymerization (A) and ATRP (B). Reproduced with permission from ref (1).

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This paper made it clear that the polymerization did not occur via a coordination–insertion reaction, nor was it a redox initiated conventional radical polymerization or a degenerative transfer process. Coordination–insertion was eliminated by the similarities in stereochemistry mentioned above as well as the effectiveness of radical inhibitors (galvinoxyl) in stopping the reaction. The reaction could not proceed via conventional radical polymerization because molecular mass increased with conversion, indicating fast initiation and controlled propagation of chains. Telomerization via degenerative chain transfer was discredited by the linear dependence of molecular mass on conversion.

There were early experiments in this paper that alluded to contributing factors that would be studied in much more depth later: for example, the effect of the alkyl halide initiator structure and the observable difference between working with chlorine and bromine as the leaving group. There were indications of the effects of solvation and ligand effects on the halogen exchange equilibrium and radical concentration. Despite the simplicity of the basic mechanistic scheme, decades of more research, up to the present day, into mechanism and polymerization control have led to new polymerization systems and expanded the range of monomers that can be polymerized by atom transfer radical systems. During this time, controlled radical polymerization (CRP) emerged as its own field of study and would later become known as reversible deactivation radical polymerization (RDRP).

In fact, some controversy over the mechanism of ATRP would consume the field for years after 1995. It was in part the great success of strategies based on the findings of this paper which solidified its results as the correct reaction mechanism. The choice of initiator structure and halogen, and the use of strategic design to control both solubility and exchange equilibria of the catalyst, remove competing inhibitors, and reduce the amount of catalyst in the system, have been the dominant strategies for chemical innovation in ATRP. (16)

By demonstrating in one paper that one simple catalyst was controlling chain growth via radical propagation in a range of monomers, this report achieved two big shifts in polymer science. The first was that a broad palette of radically polymerizable monomers and their copolymers could be polymerized by ATRP to yield well-defined polymers. The second was that perhaps anyone could conduct a living polymerization in their own laboratory using commercially available chemicals and (maybe) without much experience in synthetic chemistry. A great democratization of polymer chemistry was started. ATRP would be complemented by major progress in nitroxide mediated polymerization (NMP) and later reversible addition–fragmentation chain-transfer polymerization (RAFT). These methods in combination with the adoption of “click” chemistry provided an easy-to-use tool kit to an enormous range of disciplines, whose researchers could deliberately prepare and study tailored, functional macromolecules and structured soft materials. Another great advantage of these chemistries, which was clear very early with ATRP, was the presence of easily transformable end groups. Conversion of the alkyl halide end group, and the ability to use a wide range of functional initiators and monomers due to the high tolerance of radical reactions, meant that all kinds of architecture variants (stars, branches, telechelics, and even cyclics) could be produced as well. Today, any physicist, medical researcher, or engineer can use RDRP, often ATRP, in their own laboratory and access seemingly endless variations of copolymer chemistries and molecular architectures. (17)

I do not think that one can overstate how important the development of ATRP, and RDRP more generally, has been to the broader fields of science. Alvin Weinberg, once Director of Oak Ridge National Laboratory, wrote in an editorial on priority investments in research “that field has the most scientific merit which contributes most heavily to and illuminates most brightly its neighboring scientific disciplines.” (18) Certainly, the RDRP tool kit has been a powerful enabler of our fundamental understanding of condensed matter physics. Beyond that, polymers produced from RDRP are used in fields ranging from medicine to agriculture: anywhere that precision control of chain structure and amphiphilic properties improves performance, such as adhesives, drug delivery, biocompatibilization, composites, pigment dispersion, and manufacturing processes for memory devices, among others. These research fields have all been advanced by the accessibility and flexibility of RDRP methods. In all of these fields it is the ability to dramatically reduce and fine-tune the distributions of molecular properties including molecular mass, chemical functionality, and architecture that has imparted precise control of higher-order structure and the resulting thermodynamics and transport properties in polymer thin films, solutions, and solids.

After those exciting communications reporting the discovery of ATRP, it was this full paper that solidified 1995 as the year that spark of an idea became a flame.

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    • Notes
      Views expressed in this editorial are those of the author and not necessarily the views of the ACS.
      The author declares no competing financial interest.

    Acknowledgments

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    Drs. Beers is writing in her personal capacity and the views expressed in the article/editorial do not necessarily represent the views of NIST or the United States. Conversations and suggestions from Dr. Timothy E. Patten are gratefully acknowledged.

    References

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    This article references 18 other publications.

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    Macromolecules

    Cite this: Macromolecules 2020, 53, 4, 1115–1118
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    https://doi.org/10.1021/acs.macromol.9b02460
    Published February 25, 2020

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    • Figure 1

      Figure 1. Participants at a 1995 Symposium at the Romanian Academy in Iasi. Professor Matyjaszewski is fourth from the right, Professor Percec is fifth, and Professor Sawamoto is sixth. All three would publish communications reporting controlled radical polymerization based on transition metal mediated halogen exchange in 1995, leading up to the full paper discussed in this editorial. Reproduced with permission from ref (11). Copyright 2018 Royal Society of Chemistry.

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      Figure 2

      Figure 2. Reproduction of Figure 6 from ref (1) comparing 13C NMR of PMMA prepared via conventional radical polymerization (A) and ATRP (B). Reproduced with permission from ref (1).

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    • References

      This article references 18 other publications.

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        Wang, J. S.; Matyjaszewski, K. Controlled/“Living” Radical Polymerization. Halogen Atom Transfer Radical Polymerization Promoted by a Cu(I)/Cu(II) Redox Process. Macromolecules 1995, 28 (23), 7901– 7910,  DOI: 10.1021/ma00127a042
        1
        Controlled/"Living" Radical Polymerization. Halogen Atom Transfer Radical Polymerization Promoted by a Cu(I)/Cu(II) Redox Process
        Wang, Jin-Shan; Matyjaszewski, Krzysztof
        Macromolecules (1995), 28 (23), 7901-10CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
        An extension of atom transfer radical addn., ATRA, to atom transfer radical polymn., ATRP, provided a new and efficient way to conduct controlled/". By using a simple alkyl halide, R-X (X = Cl and Br), as an initiator and a transition metal species complexed by suitable ligand(s), Mtn/Lx, e.g., CuX/2,2'-bipyridine, as a catalyst, ATRP of vinyl monomers such as styrenes and (meth)acrylates proceeded in a living fashion, yielding polymers with d.p. predetd. by Δ[M]/[I]0 up to Mn ≈ 105 and low polydispersities, 1.1 < Mw/Mn < 1.5. The participation of free radical intermediates was supported by anal. of the end groups and the stereochem. of the polymn. The general principle and the mechanism of ATRP are elucidated. Various factors affecting the ATRP process are discussed.
      2. 2
        Matyjaszewski, K.; Wang, J. S. Novel (Co)Polymers and a Novel Polymerization Process Based on Atom (or Group) Transfer Radical Polymerization. US 5763548, 1995.
        There is no corresponding record for this reference.
      3. 3
        Cationic Polymerizations: Mechanism, Synthesis, and Applications; Matyjaszewski, K., Ed.; Marcel Dekker: New York, 1996.
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        Aoshima, S.; Kanaoka, S. A Renaissance in Living Cationic Polymerization. Chem. Rev. 2009, 109 (11), 5245– 5287,  DOI: 10.1021/cr900225g
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        A Renaissance in Living Cationic Polymerization
        Aoshima, Sadahito; Kanaoka, Shokyoku
        Chemical Reviews (Washington, DC, United States) (2009), 109 (11), 5245-5287CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
        A review discussing advances in living cationic polymn. initiators, including the design and synthesis of a variety of new polymers, with focus on the most recent developments. Many innovative breakthroughs and developments have been seen, and the future of this field looks very promising. Polymn. of a large no. of monomers is described, with emphasis on novel monomers and prepn. of block and end-functionalized polymers of various chain structure. A lot of very interesting research is also happening in the fascinating field of photoinduced or thermally induced cationic polymnl by latent initiators, cationic ring-opening polymn. of heterocyclic compds., etc. Therefore, it is suggested that this review be read in combination with other review papers as well.
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        Webster, O. W. Living Polymerization Methods. Science (Washington, DC, U. S.) 1991, 251 (4996), 887– 893,  DOI: 10.1126/science.251.4996.887
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        Living polymerization methods
        Webster, Owen W.
        Science (Washington, DC, United States) (1991), 251 (4996), 887-93CODEN: SCIEAS; ISSN:0036-8075.
        A review with 59 refs. on living polymn. methods. General features of living polymn. and methods including anionic, cationic, covalent, and free-radical living polymns. are reviewed and discussed with respect to prepn. of polymers with controlled architecture (e.g., block, comb, ladder, etc.).
      6. 6
        Otsu, T.; Yoshida, M.; Kuriyama, A. Living Radical Polymerizations in Homogeneous Solution by Using Organic Sulfides as Photoiniferters. Polym. Bull. 1982, 7 (1), 45– 50,  DOI: 10.1007/BF00264156
        6
        Living radical polymerizations in homogeneous solution by using organic sulfides as photoiniferters
        Otsu, Takayuki; Yoshida, Masatoshi; Kuriyama, Akira
        Polymer Bulletin (Berlin, Germany) (1982), 7 (1), 45-50CODEN: POBUDR; ISSN:0170-0839.
        Polystyrene was prepd. by living radical polymn. in homogeneous soln. using 4 org. sulfide initiator-transfer agent-terminators (photoiniferters). styrene [100-42-5] Photopolymd, with diphenyl disulfide (I) [882-33-7], tetraethylthiuram disulfide [97-77-8], benzyl diethyldithiocarbamate [3052-61-7] and 2-phenylethyl diethyldithiocarbamate [3052-60-6] gave polymers with yields and av.-mol. wts. increased as a function of the reaction time. These polymns. proceeded via a living radical mechanism. When these photoiniferters except I were used, the propagating polymer chain end was always the Et2NCSS group, which can further photodissoc. into a reactive propagating radical and a less reactive small radical Et2NCSS· in order to result in successive insertion of monomer mols. into the dissocd. bond.
      7. 7
        Solomon, D. H.; Rizzardo, E.; Cacioli, P. Free Radical Polymerization and the Produced Polymers. EP135280A2, 1985.
        There is no corresponding record for this reference.
      8. 8
        Solomon, D. H.; Rizzardo, E.; Cacioli, P. Polymerization Process and Polymers Produced Thereby. US 4581429, 1986.
        There is no corresponding record for this reference.
      9. 9
        Johnson, C. H. J.; Moad, G.; Solomon, D. H.; Spurling, T. H.; Vearing, D. J. The Application of Supercomputers in Modeling Chemical Reaction Kinetics: Kinetic Simulation of ‘Quasi-Living’ Radical Polymerization. Aust. J. Chem. 1990, 43 (7), 1215– 1230,  DOI: 10.1071/CH9901215
        9
        The application of supercomputers in modeling chemical reaction kinetics: kinetic simulation of 'quasi-living' radical polymerization
        Johnson, Charles H. J.; Moad, Graeme; Solomon, David H.; Spurling, Thomas H.; Vearing, Darren J.
        Australian Journal of Chemistry (1990), 43 (7), 1215-30CODEN: AJCHAS; ISSN:0004-9425.
        A computer program was written which employs an implicit Euler method to solve directly the complete set of coupled differential equations which result from an anal. of polymn. kinetics. The program was written to make full use of the speed and power of modern supercomputers, and is suited to the soln. of very large stiff systems of differential equations. The benefit of treating each propagation step as a discrete reaction is that information on the evolution of the mol. wt. distribution is obtained directly without the need to make perhaps unjustified assumptions such as the steady-state approxn. The method was applied in the kinetic simulation of quasi-living radical polymn. to assess the effect of exptl. variables on the mol. wt., mol. wt. distribution, and rate of polymn. Quasi-living radical polymn. can produce polymers with polydispersities approaching those obtained with anionic living polymns. Some necessary conditions for the formation of polymers with narrow mol. wt. distribution are defined.
      10. 10
        Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K. Narrow Molecular Weight Resins by a Free-Radical Polymerization Process. Macromolecules 1993, 26 (11), 2987– 2988,  DOI: 10.1021/ma00063a054
        10
        Narrow molecular weight resins by a free-radical polymerization process
        Georges, Michael K.; Veregin, Richard P. N.; Kazmaier, Peter M.; Hamer, Gordon K.
        Macromolecules (1993), 26 (11), 2987-8CODEN: MAMOBX; ISSN:0024-9297.
        Polystyrene and butadiene-styrene copolymer with polydispersities below the free-radical polymn. theor. limit of 1.5 are prepd. The process comprises heating the monomer mixt. in the presence of a free-radical initiator (Bz2O2) and a stable free radical (TEMPO). The TEMPO/Bz2O2 ratio affects the reaction rate and the polydispersity of the resin. The reaction mechanism is discussed.
      11. 11
        Klein, M. L.; Percec, V. Frontiers of Macromolecular and Supramolecular Science Symposia. Polym. Chem. 2018, 9 (18), 2355– 2358,  DOI: 10.1039/C8PY90063A
        11
        Frontiers of Macromolecular and Supramolecular Science symposia
        Klein, Michael L.; Percec, Virgil
        Polymer Chemistry (2018), 9 (18), 2355-2358CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
        Frontiers of Macromol. and Supramol. Science is the name given to a symposium series created in 2008, under the name Frontiers of Macromol. Science, and continued under the new extended name. This symposium is based only on invited plenary speakers and is held under the auspices of the Romanian Academy of Science, to celebrate the life and achievements of Professor Christofor I. Simionescu, who was Director of the Petru Poni Institute of Macromol. Chem. in Iasi, Romania, for 30 years (1970-2000). During this time, Simionescu promoted intense research activity and advanced the field of org. and macromol. chem. over several domains including the chem. of wood, cellulose materials and polysaccharides, the synthesis of new initiators, new monomers and polymns., mechano-chem. of polymers, plasma-chem. and origins of life, electro-initiated polymns., and macromol. charge-transfer complexes (CTC). He developed the chem. for the synthesis of acetylenic macromol. compds. and derivs. with photoconductive properties, and elaborated the conduction theory in org. compds. As the name of the series implies, the symposia have featured, from the outset, frontier science. Importantly, participating plenary speakers have included the leaders of macromol. science from the USA, Europe, and Asia. The symposia, which are typically held in the Romanian Academy in Bucharest, as well as in the Romanian Academy's Petru Poni Institute in Iasi, provide a fitting and continuing tribute to Professor Christofor I. Simionescu, the founding father of Macromol. Science in Romania.
      12. 12
        Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T. Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris-(Triphenylphosphine)Ruthenium(II)/ Methylaluminum Bis(2,6-Di-Tert-Butylphenoxide) Initiating System: Possibility of Living Radical Polymerization. Macromolecules 1995, 28 (5), 1721– 1723,  DOI: 10.1021/ma00109a056
        12
        Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris- (triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization
        Kato, Mitsuru; Kamigaito, Masami; Sawamoto, Mitsuo; Higashimura, Toshinobu
        Macromolecules (1995), 28 (5), 1721-3CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
        Living radical polymn. of Me methacrylate (MMA) was achieved in toluene at 60° with an initiating system that consists of CCl4, RuCl2(PPh3)3, and methylaluminum bis(2,6-di-tert-butylphenoxide) (I). The no.-av. mol. wt. (‾Mn) of the polymer increased in near proportion to monomer conversion and was almost inversely proportional to the initial concn. of CCl4. The mol. wt. distribution was fairly narrow (‾Mw/‾Mn ∼ 1.3). The living nature of the polymn. was further demonstrated by monomer-addn. expts., where ‾Mn further increased with conversion, upon addn. of a fresh MMA feed to an almost completely polymd. system. This polymn. is considered to proceed via repeating radical addn. of MMA to a CCl4-derived growing end having a carbon-chlorine bond, catalyzed by RuCl2(PPh3)3 and I.
      13. 13
        Wang, J. S.; Matyjaszewski, K. Controlled/“Living” Radical Polymerization. Atom Transfer Radical Polymerization in the Presence of Transition-Metal Complexes. J. Am. Chem. Soc. 1995, 117 (20), 5614– 5615,  DOI: 10.1021/ja00125a035
        13
        Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes
        Wang, Jin-Shan; Matyjaszewski, Krzysztof
        Journal of the American Chemical Society (1995), 117 (20), 5614-15CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
        Atom transfer radical polymn. of styrene and Me acrylate is investigated using 1-phenylethyl chloride as a chlorine atom transfer precursor (initiator) and CuCl/2,2'-bipyridine complex as a chlorine atom transfer promoter (catalyst). The "living" radical polymn. of styrene alone generates polymers with predetd. mol. wt. up to Mn ≈ 105 and with narrow mol. wt. distribution. Block copolymers of styrene and Me acrylate are also synthesized using the same technique.
      14. 14
        Wang, J. S.; Matyjaszewski, K. Living”/Controlled Radical Polymerization. Transition-Metal-Catalyzed Atom Transfer Radical Polymerization in the Presence of a Conventional Radical Initiator. Macromolecules 1995, 28 (22), 7572– 7573,  DOI: 10.1021/ma00126a041
        14
        "Living"/Controlled Radical Polymerization. Transition-Metal-Catalyzed Atom Transfer Radical Polymerization in the Presence of a Conventional Radical Initiator
        Wang, Jin-Shan; Matyjaszewski, Krzysztof
        Macromolecules (1995), 28 (22), 7572-3CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
        A novel type of atom transfer radical polymn., ATRP, initiated with AIBN/cuIICl2/bpy affords the bulk polymn. of styrene at 130° in a "living"/controlled manner, similar to the one with R-X/CuI/bpy reported earlier. Moreover, a "living"/controlled ATRP of Me acrylate at 130° was accomplished, when a catalytic amt. of AIBN (1% molar equiv.) was combined with 2-chloropropionitrile (initiator) in the presence of bpy/CuIICl2.
      15. 15
        Percec, V.; Barboiu, B. Living” Radical Polymerization of Styrene Initiated by Arenesulfonyl Chlorides and CuI(Bpy)NCl. Macromolecules 1995, 28 (23), 7970– 7972,  DOI: 10.1021/ma00127a057
        15
        "Living" Radical Polymerization of Styrene Initiated by Arenesulfonyl Chlorides and CuI(bpy)nCl
        Percec, Virgil; Barboiu, Bogdan
        Macromolecules (1995), 28 (23), 7970-2CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
        Revised mechanism of "living" radical polymn. of styrene initiated by arenesulfonyl chlorides and in situ formed CuCl-bipyridine complexes is presented. A wide range of functional groups (F, Cl, NO2, MeO, etc.) can be introduced as chain ends of polystyrene from arenesulfonyl chlorides.
      16. 16
        Matyjaszewski, K. Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives. Macromolecules 2012, 45 (10), 4015– 4039,  DOI: 10.1021/ma3001719
        16
        Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives
        Matyjaszewski, Krzysztof
        Macromolecules (Washington, DC, United States) (2012), 45 (10), 4015-4039CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
        A review. Current status and future perspectives in atom transfer radical polymn. (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP. New hybrid materials based on org./inorg. systems and natural/synthetic polymers are presented. Some current and forthcoming applications are described.
      17. 17
        Matyjaszewski, K. Advanced Materials by Atom Transfer Radical Polymerization. Adv. Mater. 2018, 30 (23), 1– 22,  DOI: 10.1002/adma.201706441
        There is no corresponding record for this reference.
      18. 18
        Weinberg, A. M. Criteria for Scientific Choice. Phys. Today 1964, 17 (3), 42,  DOI: 10.1063/1.3051468
        There is no corresponding record for this reference.