Stereo-, Temporal and Chemical Control through Photoactivation of Living Radical Polymerization: Synthesis of Block and Gradient Copolymers

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This article references 117 other publications.

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   Macromolecular Engineering by Atom Transfer Radical Polymerization

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   A review. This Perspective presents recent advances in macromol. engineering enabled by ATRP. They include the fundamental mechanistic and synthetic features of ATRP with emphasis on various catalytic/initiation systems that use parts-per-million concns. of Cu catalysts and can be run in environmentally friendly media, e.g., water. The roles of the major components of ATRP-monomers, initiators, catalysts, and various additives-are explained, and their reactivity and structure are correlated. The effects of media and external stimuli on polymn. rates and control are presented. Some examples of precisely controlled elements of macromol. architecture, such as chain uniformity, compn., topol., and functionality, are discussed. Syntheses of polymers with complex architecture, various hybrids, and bioconjugates are illustrated. Examples of current and forthcoming applications of ATRP are covered. Future challenges and perspectives for macromol. engineering by ATRP are discussed.

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   RAFT Polymerization and Some of its Applications

   Moad, Graeme; Rizzardo, Ezio; Thang, San H.

   Chemistry - An Asian Journal (2013), 8 (8), 1634-1644CODEN: CAAJBI; ISSN:1861-4728. (Wiley-VCH Verlag GmbH & Co. KGaA)

   A review. Reversible addn.-fragmentation chain transfer (RAFT) is one of the most robust and versatile methods for controlling radical polymn. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to the majority of monomers subject to radical polymn. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes. In this Focus Review we describe how the development of RAFT and RAFT application has been facilitated by the adoption of continuous flow techniques using tubular reactors and through the use of high-throughput methodol. Applications described include the use of RAFT in the prepn. of polymers for optoelectronics, block copolymer therapeutics, and star polymer rheol. control agents.

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   Ultrafast Synthesis of Ultrahigh Molar Mass Polymers by Metal-Catalyzed Living Radical Polymerization of Acrylates, Methacrylates, and Vinyl Chloride Mediated by SET at 25 °C

   Percec, Virgil; Guliashvili, Tamaz; Ladislaw, Janine S.; Wistrand, Anna; Stjerndahl, Anna; Sienkowska, Monika J.; Monteiro, Michael J.; Sahoo, Sangrama

   Journal of the American Chemical Society (2006), 128 (43), 14156-14165CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

   Conventional metal-catalyzed org. radical reactions and living radical polymns. (LRP) performed in nonpolar solvents, including atom-transfer radical polymn. (ATRP), proceed by an inner-sphere electron-transfer mechanism. One catalytic system frequently used in these polymns. is based on Cu(I)X species and N-contg. ligands. Here, it is reported that polar solvents such as H2O, alcs., dipolar aprotic solvents, ethylene and propylene carbonate, and ionic liqs. instantaneously disproportionate Cu(I)X into Cu(0) and Cu(II)X2 species in the presence of a diversity of N-contg. ligands. This disproportionation facilitates an ultrafast LRP in which the free radicals are generated by the nascent and extremely reactive Cu(0) at. species, while their deactivation is mediated by the nascent Cu(II)X2 species. Both steps proceed by a low activation energy outer-sphere single-electron-transfer (SET) mechanism. The resulting SET-LRP process is activated by a catalytic amt. of the electron-donor Cu(0), Cu2Se, Cu2Te, Cu2S, or Cu2O species, not by Cu(I)X. This process provides, at room temp. and below, an ultrafast synthesis of ultrahigh mol. wt. polymers from functional monomers contg. electron-withdrawing groups such as acrylates, methacrylates, and vinyl chloride, initiated with alkyl halides, sulfonyl halides, and N-halides.

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    Microtacticity of poly(methacrylic acid esters) obtained by radical polymerization

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    The stereoregularity of different polymethacrylate esters depends on the bulkiness and the polarizability of the ester group. Phenyl, β-naphthyl, p-tert-butylphenyl, neopentyl, p-chlorophenyl, menthyl, and triethylmethyl methacrylates were prepd. by treating methacrylyl chloride with the corresponding Na alcoholate or phenolate. Cyclohexyl, decahydro-β-naphthyl, and p-tert-butylcyclohexyl methacrylates were prepd. by ester exchange between Me methacrylate and the alc. Trityl methacrylate was prepd. from Ag methacrylate and trityl chloride. The methacrylates were polymd. by radical initiated polymn. and the microtacticity of the polymers was detd. by high resolution NMR. The syndiotacticity decreased systematically from poly(Me methacrylate) [9011-14-7] to poly(triethylmethyl methacrylate) [34032-79-6] in the series of satd. polymers. The aromatic polymethacrylates had a lower syndiotacticity than the corresponding satd. polymers. In poly(trityl methacrylate) [27497-74-1], bulkiness and interaction are important and the polymer is isotactic.

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    The steric effect of ester groups on stereoregularity of polymethacrylates (such as poly(phenyl methacrylate) [25189-01-9], poly(benzyl methacrylate) [25085-83-0], poly(2-phenylethyl methacrylate) [28825-60-7], etc.) initiated by Grignard reageants was investigated. Syndiotacticity and isotacticity decreased with increasing steric factor.

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    Pronounced effects of temperature and monomer concentration on isotactic specificity of triphenylmethyl methacrylate polymerization through free radical mechanism. Thermodynamic versus kinetic control of propagation stereochemistry

    Nakano, Tamaki; Matsuda, Akihiro; Okamoto, Yoshio

    Polymer Journal (Tokyo) (1996), 28 (6), 556-558CODEN: POLJB8; ISSN:0032-3896. (Society of Polymer Science, Japan)

    Polymers having a wide range of tacticity were obtained by changing the polymn. temp. and the monomer concn. in feed [M]0 in triphenylmethyl methacrylate polymn. At a higher polymn. temp. and at a lower [M]0, a higher isotacticity was achieved. At a higher temp. and a lower [M]0, the reaction was mediated predominantly by the more stable growing radical (thermodn. control) and under the reversed conditions, predominantly by the less stable growing radical formed on monomer addn. (kinetic control). Solvent also affected the reaction stereochem.

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44. 44

    Otsu, T.; Yamada, B.; Sugiyama, S.; Mori, S. J. Polym. Sci., Polym. Chem. Ed. 1980, 18, 2197– 2207 DOI: 10.1002/pol.1980.170180715

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    Effects of ortho-substituents on reactivities, tacticities, and ceiling temperatures of radical polymerizations of phenyl methacrylates

    Otsu, Takayuki; Yamada, Bunichiro; Sugiyama, Shigeru; Mori, Shigeki

    Journal of Polymer Science, Polymer Chemistry Edition (1980), 18 (7), 2197-207CODEN: JPLCAT; ISSN:0360-6376.

    The effects of ortho substituents on reactivity, tacticity, thermal stability, and ceiling temp. in the polymn. of phenyl methacrylates was detd. Monomer reactivity was decreased by ortho substituents. 2,6-Di-tert-butylphenyl methacrylate [74939-18-7] formed no MeOH-insol. polymer at 60°. Ortho-substituted phenyl methacrylates underwent syndiotactic addn. in propagation less than did Ph methacrylate (I) [2177-70-0]. Polymers formed from the substituted monomers were thermally less stable than I polymer; and ceiling temps. of substituted monomers were lower than that of I. These effects were caused by the conformational proximity of substituents to the double bond or the C carrying the unpaired electron of the polymer radical.

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45. 45

    Yuki, H.; Okamoto, Y.; Shimada, Y.; Ohta, K.; Hatada, K. Polymer 1976, 17, 618– 622 DOI: 10.1016/0032-3861(76)90280-9

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    Okamoto, Y.; Ishikura, M.; Hatada, K.; Yuki, H. Polym. J. 1983, 15, 851– 853 DOI: 10.1295/polymj.15.851

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    Stereospecific and asymmetric polymerization of diphenylpyridylmethyl methacrylates

    Okamoto, Yoshio; Ishikura, Motoshi; Hatada, Koichi; Yuki, Heimei

    Polymer Journal (Tokyo, Japan) (1983), 15 (11), 851-3CODEN: POLJB8; ISSN:0032-3896.

    Diphenyl-2-pyridiylmethyl methacrylate (I) [88718-71-2], which was prepd. from methacryloyl chloride [920-46-7] and Na diphenyl-2-pyridiylmethoxide [89035-07-4], gave by radical polymn. in the presence of AIBN [78-67-1] a polymer (II) [89054-47-7] (yield 36%) having d.p. 95 and isotacticity 86%, and by anionic polymn. in the presence of BuLi II (yield 56%) having d.p. 675 and isotacticity 94%. Polymn. of I by chiral anionic initiators (-)-sparteine-BuLi complex and (2R, 3R)-(-)-2,3-dimethoxy-1,4-bis(dimethylamino)butane-N,N'-diphenylethylenediamine monolithium amide complex gave optically active II (yield 94-100%) having d.p. 62-398 and isotacticity 91-95%. Diphenyl-4-pyridylmethyl methacrylate (III) [85328-09-2], which was prepd. from Ag methacrylate [16631-02-0] and diphenyl-4-pyridylmethyl chloride [42362-54-9], gave in the presence of AIBN a polymer (IV) [87335-87-3] (yield 15%) having d.p. 47 and isotacticity 76%, and in the presence of BuLi IV (yield 53%) having d.p. 55 and isotacticity 90%. Polymn of III in the presence of the above chiral initiators gave optically active IV (yield 78-85%) having d.p. 45-93 and isotacticity 68-94%.

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47. 47

    Nakano, T.; Kinjo, N.; Hidaka, Y.; Okamoto, Y. Polym. J. 2001, 33, 306– 309 DOI: 10.1295/polymj.33.306

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    Asymmetric anionic and free-radical polymerization of 10,10-dimethyl- and 10,10-dibutyl-9-phenyl-9,10-dihydroanthracen-9-yl methacrylate leading to single-handed helical polymers

    Nakano, Tamaki; Kinjo, Naotaka; Hidaka, Yasuaki; Okamoto, Yoshio

    Polymer Journal (Tokyo, Japan) (2001), 33 (3), 306-309CODEN: POLJB8; ISSN:0032-3896. (Society of Polymer Science, Japan)

    In the present study, two novel triarylmethyl methacrylates having fused ring structures including a six-membered ring, namely, 10, 10-dimethyl-9-phenyl-9, 10-dihydroanthracen-9-yl methacrylate (DMPAMA), and 10,10-dibutyl-9-phenyl-9, 10-dihydroanthracen-9-yl methacrylate (DBPAMA), were polymd. under anionic and radical reaction conditions. The radical polymn. of 9-phenylfluoren-9-yl methacrylate (PFMA) was also performed. The asym. anionic polymn. of DMPAMA and DBPAMA led to highly isotactic, optically active polymers having a single-handed helical conformation. It was suggested that the high optical activity of the poly(triarylmethyl methacrylate)s may be partly based on the single-handed propeller conformation in addn. to the main-chain helix. The radical polymn. of DMPAMA and DBPAMA resulted in the isotactic polymer formation while PFMA gave atactic polymers, suggesting that the polymn. stereochem. is sensitive to the monomer structure. The helix-sense selection was achieved during the radical polymn. of DBPAMA in the presence of an optically active chain-transfer agent. Poly(DBPAMA)s with high mol. wt. showed much better soly. than the other helical polymethacrylates.

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    Enantioselective Radical Processes

    Sibi, Mukund P.; Manyem, Shankar; Zimmerman, Jake

    Chemical Reviews (Washington, DC, United States) (2003), 103 (8), 3263-3295CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)

    A review on stereoselective radical reactions, such as hydrogen transfer reactions, reductive alkylations, and oxidns.

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50. 50

    Hopkins, T. E.; Wagener, K. B. Adv. Mater. 2002, 14, 1703– 1715 DOI: 10.1002/1521-4095(20021203)14:23<1703::AID-ADMA1703>3.0.CO;2-5

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    Polymerization of cholesteryl methacrylate in the mesophase

    Saeki, Hideo; Iimura, Kazuyoshi; Takeda, Masatami

    Polymer Journal (Tokyo, Japan) (1972), 3 (3), 414-16CODEN: POLJB8; ISSN:0032-3896.

    The mesomorphic temp. decreased as the polymn. proceeded in an investigation of the thermal polymn. of cholesteryl methacrylate (I) [35109-51-4]. Upon heating, I melted to a transparent liq. at 108-110.deg.. Upon cooling, a blue color appeared at 108-4.deg. and I became an opaque solid at 90-85.deg.. A weak differential scanning calorimetry peak at 103.deg. was ascribed to a transition from the isotropic liq. to the cholesteric mesophase.

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    Synthesis and tacticity characterization of a novel series of liquid-crystalline side chain polymers with oligo(ethylene oxide) spacers

    Duran, Randolph; Gramain, Philippe

    Makromolekulare Chemie (1987), 188 (8), 2001-9CODEN: MACEAK; ISSN:0025-116X.

    A series of liq.-cryst. side-chain (meth)acrylic polymers contg. oligo(ethylene oxide) spacers was synthesized and characterized. Although all polymers were polymd. free radically, NMR tacticity studies showed a systematic variation of the obsd. tacticity of the methacrylate series, the isotactic content decreasing with increasing spacer length. The data indicated that the spacer length and mesogenic group play a role in detg. microstructure during polymn.

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    Nakano, T.; Hasegawa, T.; Okamoto, Y. Macromolecules 1993, 26, 5494– 5502 DOI: 10.1021/ma00072a030

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    Koltzenburg, S.; Wolff, D.; Springer, J.; Nuyken, O. J. Polym. Sci., Part A: Polym. Chem. 1998, 36, 2669– 2679 DOI: 10.1002/(SICI)1099-0518(19981115)36:15<2669::AID-POLA1>3.0.CO;2-4

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    Novel study on the liquid crystalline behavior of poly(methacrylate)s with biphenyl side groups

    Koltzenburg, S.; Wolff, D.; Springer, J.; Nuyken, O.

    Journal of Polymer Science, Part A: Polymer Chemistry (1998), 36 (15), 2669-2679CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)

    A of liq. cryst. polymethacrylates contg. the 4'-methoxybiphenyl-4-yloxy group and spacer length of 4-8 methylene units were prepd. and characterized by polarized light microscopy, differential scanning calorimetry, and x-ray anal. All homologues show highly ordered phases and the butylene polymer shows a broad nematic mesophase. A narrow nematic phase of the hexylene homolog could be confirmed exptl. X-ray data of the polymers was used to identify low temp. phases and arrangement of mesogenes within the layers. The pentylene homolog shows distinct deviation from the behavior of the other polymers.

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    Okamoto, Y.; Yamada, K.; Nakano, T. In Controlled/Living Radical Polymerization; American Chemical Society: Washington, D.C., 2000; Vol. 768, pp 57– 67.

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    Yamada, K.; Nakano, T.; Okamoto, Y. Macromolecules 1998, 31, 7598– 7605 DOI: 10.1021/ma980889s

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    Yamada, K.; Nakano, T.; Okamoto, Y. Proc. Jpn. Acad., Ser. B 1998, 74, 46– 49 DOI: 10.2183/pjab.74.46

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    Stereospecific polymerization of vinyl acetate in fluoroalcohols: synthesis of syndiotactic poly(vinyl alcohol)

    Yamada, Kazunobu; Nakano, Tamaki; Okamoto, Yoshio

    Proceedings of the Japan Academy, Series B: Physical and Biological Sciences (1998), 74B (3), 46-49CODEN: PJABDW; ISSN:0386-2208. (Nippon Gakushiin)

    The free-radical polymn. of vinyl acetate (VAc) was carried out in various alc. solvents. Fluoroalcs. with a lower pKa and higher bulkiness were effective in enhancing the syndiotactic specificity of the polymn. The polymn. of VAc in perfluoro-tert-Bu alc. ((CF3)3COH) at -78° led to a dyad syndiotacticity of 72%, which is the highest value reported for the radical polymn. of vinyl esters. Hydrogen-bonding between the acetyl groups of VAc and polymer and the fluoroalc. mol. may be responsible for the enhancement of the syndiotactic specific propagation.

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58. 58

    Renaud, P.; Gerster, M. Angew. Chem., Int. Ed. 1998, 37, 2562– 2579 DOI: 10.1002/(SICI)1521-3773(19981016)37:19<2562::AID-ANIE2562>3.3.CO;2-4

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    Kamigaito, M.; Satoh, K. Macromolecules 2008, 41, 269– 276 DOI: 10.1021/ma071499l

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    Kamigaito, M.; Satoh, K. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 6147– 6158 DOI: 10.1002/pola.21688

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    Stereospecific living radical polymerization for simultaneous control of molecular weight and tacticity

    Kamigaito, Masami; Satoh, Kotaro

    Journal of Polymer Science, Part A: Polymer Chemistry (2006), 44 (21), 6147-6158CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)

    A review. The simultaneous control of the mol. wts. and the tacticity was attained even during radical polymn. by the judicious combinations of the living/controlled radical polymns. based on the fast interconversion between the dormant and active species, and the stereospecific radical polymns. mediated by the added Lewis acids or polar solvents via the coordination to the monomer/polymer terminal substituents. This can be useful for various monomers including not only conjugated monomers, such as acrylamides and methacrylates, but also nonconjugated ones such as vinyl acetate and N-vinylpyrrolidone. Stereoblock polymers were easily obtained by the addn. of the Lewis acids or by change of the solvents during the living radical polymns.

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61. 61

    Kamigaito, M.; Satoh, K.; Wan, D.; Sugiyama, Y.; Koumura, K.; Shibata, T.; Okamoto, Y. In Controlled/Living Radical Polymerization; American Chemical Society: Washington, D.C., 2006; Vol. 944, pp 26– 39.

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    Leibfarth, F. A.; Mattson, K. M.; Fors, B. P.; Collins, H. A.; Hawker, C. J. Angew. Chem., Int. Ed. 2013, 52, 199– 210 DOI: 10.1002/anie.201206476

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    External Regulation of Controlled Polymerizations

    Leibfarth, Frank A.; Mattson, Kaila M.; Fors, Brett P.; Collins, Hazel A.; Hawker, Craig J.

    Angewandte Chemie, International Edition (2013), 52 (1), 199-210CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)

    A review. Polymer chemists, through advances in controlled polymn. techniques and reliable post-functionalization methods, now have the tools to create materials of almost infinite variety and architecture. Many relevant challenges in materials science, however, require not only functional polymers but also on-demand access to the properties and performance they provide. The power of such temporal and spatial control of polymn. can be found in nature, where the prodn. of proteins, nucleic acids, and polysaccharides helps regulate multicomponent systems and maintain homeostasis. Here we review existing strategies for temporal control of polymns. through external stimuli including chem. reagents, applied voltage, light, and mech. force. Recent work illustrates the considerable potential for this emerging field and provides a coherent vision and set of criteria for pursuing future strategies for regulating controlled polymns.

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63. 63

    Pauloehrl, T.; Delaittre, G.; Winkler, V.; Welle, A.; Bruns, M.; Börner, H. G.; Greiner, A. M.; Bastmeyer, M.; Barner-Kowollik, C. Angew. Chem., Int. Ed. 2012, 51, 1071– 1074 DOI: 10.1002/anie.201107095

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    Fors, B. P.; Hawker, C. J. Angew. Chem., Int. Ed. 2012, 51, 8850– 8853 DOI: 10.1002/anie.201203639

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    Control of a Living Radical Polymerization of Methacrylates by Light

    Fors, Brett P.; Hawker, Craig J.

    Angewandte Chemie, International Edition (2012), 51 (35), 8850-8853, S8850/1-S8850/15CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)

    This paper reports a new controlled living radical polymn. that displays an unprecedented response to activation and deactivation of polymn. through external visible light stimulation.

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65. 65

    Fors, B. P.; Poelma, J. E.; Menyo, M. S.; Robb, M. J.; Spokoyny, D. M.; Kramer, J. W.; Waite, J. H.; Hawker, C. J. J. Am. Chem. Soc. 2013, 135, 14106– 14109 DOI: 10.1021/ja408467b

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66. 66

    Poelma, J. E.; Fors, B. P.; Meyers, G. F.; Kramer, J. W.; Hawker, C. J. Angew. Chem., Int. Ed. 2013, 52, 6844– 6848 DOI: 10.1002/anie.201301845

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    Fabrication of Complex Three-Dimensional Polymer Brush Nanostructures through Light-Mediated Living Radical Polymerization

    Poelma, Justin E.; Fors, Brett P.; Meyers, Gregory F.; Kramer, John W.; Hawker, Craig J.

    Angewandte Chemie, International Edition (2013), 52 (27), 6844-6848CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)

    A facile approach to patterned polymer brushes has been developed by taking advantage of the temporal and spatial control afforded by a "living" visible light mediated radical polymn. Through modulation of the light intensity, complex and arbitrary 3D structures can be fabricated. Furthermore, patterned block copolymer structures can be formed for tuning surface properties.

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67. 67

    Treat, N. J.; Fors, B. P.; Kramer, J. W.; Christianson, M.; Chiu, C.-Y.; Alaniz, J. R. d.; Hawker, C. J. ACS Macro Lett. 2014, 3, 580– 584 DOI: 10.1021/mz500242a

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    Controlled Radical Polymerization of Acrylates Regulated by Visible Light

    Treat, Nicolas J.; Fors, Brett P.; Kramer, John W.; Christianson, Matthew; Chiu, Chien-Yang; Read de Alaniz, Javier; Hawker, Craig J.

    ACS Macro Letters (2014), 3 (6), 580-584CODEN: AMLCCD; ISSN:2161-1653. (American Chemical Society)

    The controlled radical polymn. of a variety of acrylate monomers is reported using an Ir-catalyzed visible light mediated process leading to well-defined homo-, random, and block copolymers. The polymns. could be efficiently activated and deactivated using light while maintaining a linear increase in mol. wt. with conversion and first order kinetics. The robust nature of the fac-[Ir(ppy)3] catalyst allows carboxylic acids to be directly introduced at the chain ends through functional initiators or along the backbone of random copolymers (controlled process up to 50 mol % acrylic acid incorporation). In contrast to traditional ATRP procedures, low polydispersity block copolymers, poly(acrylate)-b-(acrylate), poly(methacrylate)-b-(acrylate), and poly(acrylate)-b-(methacrylate), could be prepd. with no monomer sequence requirements. These results illustrate the increasing generality and utility of light mediated Ir-catalyzed polymn. as a platform for polymer synthesis.

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68. 68

    Treat, N. J.; Sprafke, H.; Kramer, J. W.; Clark, P. G.; Barton, B. E.; Read de Alaniz, J.; Fors, B. P.; Hawker, C. J. J. Am. Chem. Soc. 2014, 136, 16096– 16101 DOI: 10.1021/ja510389m

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    Metal-Free Atom Transfer Radical Polymerization

    Treat, Nicolas J.; Sprafke, Hazel; Kramer, John W.; Clark, Paul G.; Barton, Bryan E.; Read de Alaniz, Javier; Fors, Brett P.; Hawker, Craig J.

    Journal of the American Chemical Society (2014), 136 (45), 16096-16101CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    Overcoming the challenge of metal contamination in traditional ATRP systems, a metal-free ATRP process, mediated by light and catalyzed by an org.-based photoredox catalyst, is reported. Polymn. of vinyl monomers are efficiently activated and deactivated with light leading to excellent control over the mol. wt., polydispersity, and chain ends of the resulting polymers. Significantly, block copolymer formation was facile and could be combined with other controlled radical processes leading to structural and synthetic versatility. We believe that these new org.-based photoredox catalysts will enable new applications for controlled radical polymns. and also be of further value in both small mol. and polymer chem.

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69. 69

    Konkolewicz, D.; Schröder, K.; Buback, J.; Bernhard, S.; Matyjaszewski, K. ACS Macro Lett. 2012, 1, 1219– 1223 DOI: 10.1021/mz300457e

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    Visible Light and Sunlight Photoinduced ATRP with ppm of Cu Catalyst

    Konkolewicz, Dominik; Schroder, Kristin; Buback, Johannes; Bernhard, Stefan; Matyjaszewski, Krzysztof

    ACS Macro Letters (2012), 1 (10), 1219-1223CODEN: AMLCCD; ISSN:2161-1653. (American Chemical Society)

    Photochem. induced ATRP was performed with visible light and sunlight in the presence of ppm copper catalysts. Illumination of the reaction mixt. yielded polymn. in case of 392 and 450 nm light but not for 631 nm light. Sunlight was also a viable source for the photoinduced ATRP. Control expts. suggest photoredn. of the CuII complex (ligand to metal charge transfer in the excited state), yielding a CuI complex, and a bromine radical that can initiate polymn. No photoactivation of CuI complex was detected. This implies that the mechanism of ATRP in the presence of light is a hybrid of ICAR and ARGET ATRP. The method was also used to synthesize block copolymers and polymns. in water.

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70. 70

    Pan, X.; Lamson, M.; Yan, J.; Matyjaszewski, K. ACS Macro Lett. 2015, 4, 192– 196 DOI: 10.1021/mz500834g

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    70

    Photoinduced Metal-Free Atom Transfer Radical Polymerization of Acrylonitrile

    Pan, Xiangcheng; Lamson, Melissa; Yan, Jiajun; Matyjaszewski, Krzysztof

    ACS Macro Letters (2015), 4 (2), 192-196CODEN: AMLCCD; ISSN:2161-1653. (American Chemical Society)

    Photoinduced metal-free atom transfer radical polymn. has been successfully extended to the synthesis of polyacrylonitrile (PAN) with predictable mol. wts. and low dispersities. This was achieved using phenothiazine derivs. as photoredox catalysts, which activate dormant alkyl bromides to reversibly form propagating radicals. Both 1H NMR spectroscopy and chain-end extension polymn. show highly preserved Br chain-end functionality in the synthesized PAN.

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71. 71

    Ribelli, T. G.; Konkolewicz, D.; Bernhard, S.; Matyjaszewski, K. J. Am. Chem. Soc. 2014, 136, 13303– 13312 DOI: 10.1021/ja506379s

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    Ribelli, T. G.; Konkolewicz, D.; Pan, X.; Matyjaszewski, K. Macromolecules 2014, 47, 6316– 6321 DOI: 10.1021/ma501384q

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    Anastasaki, A.; Nikolaou, V.; Brandford-Adams, F.; Nurumbetov, G.; Zhang, Q.; Clarkson, G. J.; Fox, D. J.; Wilson, P.; Kempe, K.; Haddleton, D. M. Chem. Commun. 2015, 51, 5626– 5629 DOI: 10.1039/C4CC09916H

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    Anastasaki, A.; Nikolaou, V.; Zhang, Q.; Burns, J.; Samanta, S. R.; Waldron, C.; Haddleton, A. J.; McHale, R.; Fox, D.; Percec, V.; Wilson, P.; Haddleton, D. M. J. Am. Chem. Soc. 2014, 136, 1141– 1149 DOI: 10.1021/ja411780m

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    Nikolaou, V.; Anastasaki, A.; Alsubaie, F.; Simula, A.; Fox, D. J.; Haddleton, D. M. Polym. Chem. 2015, 6, 3581– 3585 DOI: 10.1039/C5PY00406C

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    Copper(II) gluconate (a non-toxic food supplement/dietary aid) as a precursor catalyst for effective photo-induced living radical polymerisation of acrylates

    Nikolaou, Vasiliki; Anastasaki, Athina; Alsubaie, Fehaid; Simula, Alexandre; Fox, David J.; Haddleton, David M.

    Polymer Chemistry (2015), 6 (19), 3581-3585CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)

    Copper gluconate, is employed as a precursor catalyst for the photo-induced living radical polymn. of acrylates. Optimized reaction conditions for efficient ligand transfer leads to well-defined polymers within 2 h with near quant. conversions (>95%), low dispersities (D ∼ 1.16) and high end-group fidelity, as demonstrated by MALDI-ToF-MS. Addnl., in the presence of ppm concns. of NaBr, similar degree of control could also be attained by facilitating ligand exchange, furnishing narrow dispersed polymers (D < 1.12).

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76. 76

    Koumura, K.; Satoh, K.; Kamigaito, M. Macromolecules 2008, 41, 7359– 7367 DOI: 10.1021/ma801151s

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    Koumura, K.; Satoh, K.; Kamigaito, M. Polym. J. 2009, 41, 595– 603 DOI: 10.1295/polymj.PJ2009070

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    Mn2(CO)10-induced RAFT polymerization of vinyl acetate, methyl acrylate, and styrene

    Koumura, Kazuhiko; Satoh, Kotaro; Kamigaito, Masami

    Polymer Journal (Tokyo, Japan) (2009), 41 (8), 595-603CODEN: POLJB8; ISSN:0032-3896. (Society of Polymer Science, Japan)

    A dinuclear manganese complex [Mn2(CO)10] induced the controlled/living radical polymn. of various conjugated and unconjugated vinyl monomers including vinyl acetate, Me acrylate, and styrene in conjunction with dithiocarbonyl compds. [R-SC(S)Z] under weak visible light at 40°. The obtained polymers had controlled mol. wts., narrow mol. wt. distributions, and well-defined chain-end groups originating from R-SC(S)Z, as indicated by SEC, 1H NMR, and MALDI-TOF-MS analyses. The polymn. most probably proceeds via the reversible activation of the C-SC(S)Z bond by ·Mn(CO)5 via the metal-catalyzed process and/or by the carbon-centered radical species via the addn.-fragmentation chain transfer (RAFT) process.

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    Chen, M.; MacLeod, M. J.; Johnson, J. A. ACS Macro Lett. 2015, 4, 566– 569 DOI: 10.1021/acsmacrolett.5b00241

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    Visible-Light-Controlled Living Radical Polymerization from a Trithiocarbonate Iniferter Mediated by an Organic Photoredox Catalyst

    Chen, Mao; MacLeod, Michelle J.; Johnson, Jeremiah A.

    ACS Macro Letters (2015), 4 (5), 566-569CODEN: AMLCCD; ISSN:2161-1653. (American Chemical Society)

    Living radical polymn. of acrylates and acrylamides from trithiocarbonate iniferters using a compact fluorescent lamp (CFL) bulb and 10-phenylphenothiazine as an org. photoredox catalyst is reported. With this system, chain growth can be efficiently switched between "on" and "off" in response to visible light. Polymer molar masses increase linearly with conversion, and narrow molar mass distributions are obtained. The excellent fidelity of the trithiocarbonate-iniferter enables the prepn. of triblock copolymers from macro-iniferters under the same visible-light mediated protocol, using UV light without a photoredox catalyst or under traditional thermally induced RAFT conditions. We expect that the simplicity and efficiency of this metal-free, visible-light-mediated polymn. will enable the synthesis and modification of a range of materials under mild conditions.

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    Chen, M.; Johnson, J. A. Chem. Commun. 2015, 51, 6742– 6745 DOI: 10.1039/C5CC01562F

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    Tasdelen, M. A.; Çiftci, M.; Uygun, M.; Yagci, Y. In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; American Chemical Society: Washington, D.C., 2012; Vol. 1100, pp 59– 72.

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    Tasdelen, M. A.; Uygun, M.; Yagci, Y. Macromol. Rapid Commun. 2011, 32, 58– 62 DOI: 10.1002/marc.201000351

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    Ciftci, M.; Tasdelen, M. A.; Li, W.; Matyjaszewski, K.; Yagci, Y. Macromolecules 2013, 46, 9537– 9543 DOI: 10.1021/ma402058a

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    Tasdelen, M. A.; Uygun, M.; Yagci, Y. Macromol. Chem. Phys. 2010, 211, 2271– 2275 DOI: 10.1002/macp.201000445

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    Kwak, Y.; Matyjaszewski, K. Macromolecules 2010, 43, 5180– 5183 DOI: 10.1021/ma100850a

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    Frick, E.; Anastasaki, A.; Haddleton, D. M.; Barner-Kowollik, C. J. Am. Chem. Soc. 2015, 137, 6889– 6896 DOI: 10.1021/jacs.5b03048

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    Vorobii, M.; de los Santos Pereira, A.; Pop-Georgievski, O.; Kostina, N. Y.; Rodriguez-Emmenegger, C.; Percec, V. Polym. Chem. 2015, 6, 4210– 4220 DOI: 10.1039/C5PY00506J

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    Synthesis of non-fouling poly[N-(2-hydroxypropyl)methacrylamide] brushes by photoinduced SET-LRP

    Vorobii, Mariia; de los Santos Pereira, Andres; Pop-Georgievski, Ognen; Kostina, Nina Yu.; Rodriguez-Emmenegger, Cesar; Percec, Virgil

    Polymer Chemistry (2015), 6 (23), 4210-4220CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)

    Surface-initiated photoinduced single-electron transfer living radical polymn. (SET-LRP) was employed to assemble brushes of poly[N-(2-hydroxypropyl) methacrylamide] (poly(HPMA)) from Si surfaces. The linear increase in thickness of the poly(HPMA) brushes with time and the ability to prep. block copolymers indicate the living nature of this grafting-from process. Cu concns. ≥80 ppb were sufficient for this surface-initiated SET-LRP. Micropatterns of poly(HPMA) brushes on the Si surface were constructed for the first time by this method. Negligible fouling was obsd. after contact with undiluted blood plasma. This report provides the first example of nonfouling polymer brushes prepd. by SET-LRP of HPMA.

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87. 87

    Shanmugam, S.; Xu, J.; Boyer, C. Macromolecules 2014, 47, 4930– 4942 DOI: 10.1021/ma500842u

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88. 88

    Xu, J.; Jung, K.; Atme, A.; Shanmugam, S.; Boyer, C. J. Am. Chem. Soc. 2014, 136, 5508– 5519 DOI: 10.1021/ja501745g

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    Xu, J.; Jung, K.; Boyer, C. Macromolecules 2014, 47, 4217– 4229 DOI: 10.1021/ma500883y

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    (a) Xu, J.; Jung, K.; Corrigan, N. A.; Boyer, C. Chem. Sci. 2014, 5, 3568– 3575 DOI: 10.1039/C4SC01309C

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    Aqueous photoinduced living/controlled polymerization: tailoring for bioconjugation

    Xu, Jiangtao; Jung, Kenward; Corrigan, Nathaniel Alan; Boyer, Cyrille

    Chemical Science (2014), 5 (9), 3568-3575CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)

    We report a photoinduced living polymn. technique able to polymerize a large range of monomers, including methacrylates, acrylates and acrylamides, in water and biol. media as well as org. solvents. This polymn. technique employs ultra-low concns. of a ruthenium-based photoredox catalyst (typically 1 ppm to monomers) and enables low energy visible LED light to afford well-defined polymers with narrow polydispersities (Mw/Mn < 1.3). In this paper, different parameters, including photocatalyst concns. and solvent effects, were thoroughly investigated. In addn., successful polymns. in biol. media have been reported with good control of the mol. wts. and mol. wt. distributions (Mw/Mn < 1.4). Finally, protein-polymer bioconjugates using a 'grafting from' approach were demonstrated using bovine serum albumin as a model biomacromol. The enzymic bioactivity of the protein was demonstrated to be maintained using a std. assay.

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    (b) Shanmugam, S.; Xu, J.; Boyer, C. J. Am. Chem. Soc. 2015, 137, 9174– 9185 DOI: 10.1021/jacs.5b05274

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    90b

    Exploiting Metalloporphyrins for Selective Living Radical Polymerization Tunable over Visible Wavelengths

    Shanmugam, Sivaprakash; Xu, Jiangtao; Boyer, Cyrille

    Journal of the American Chemical Society (2015), 137 (28), 9174-9185CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    The use of metalloporphyrins has been gaining popularity particularly in the area of medicine concerning sensitizers for the treatment of cancer and dermatol. diseases through photodynamic therapy (PDT), and advanced materials for engineering mol. antenna for harvesting solar energy. In line with the myriad functions of metalloporphyrins, we investigated their capability for photoinduced living polymn. under visible light irradn. over a broad range of wavelengths. We discovered that zinc porphyrins (i.e., zinc tetraphenylporphine (ZnTPP)) were able to selectively activate photoinduced electron transfer-reversible addn.-fragmentation chain transfer (PET-RAFT) polymn. of trithiocarbonate compds. for the polymn. of styrene, (meth)acrylates and (meth)acrylamides under a broad range of wavelengths (from 435 to 655 nm). Interestingly, other thiocarbonylthio compds. (dithiobenzoate, dithiocarbamate and xanthate) were not effectively activated in the presence of ZnTPP. This selectivity was likely attributed to a specific interaction between ZnTPP and trithiocarbonates, suggesting novel recognition at the mol. level. This interaction between the photoredox catalyst and trithiocarbonate group confers specific properties to this polymn., such as oxygen tolerance, enabling living radical polymn. in the presence of air and also ability to manipulate the polymn. rates (kpapp from 1.2-2.6 × 10-2 min-1) by varying the visible wavelengths.

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91. 91

    Xu, J.; Shanmugam, S.; Duong, H. T.; Boyer, C. Polym. Chem. 2015, 6, 5615– 5624 DOI: 10.1039/C4PY01317D

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    91

    Organo-photocatalysts for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization

    Xu, Jiangtao; Shanmugam, Sivaprakash; Duong, Hien T.; Boyer, Cyrille

    Polymer Chemistry (2015), 6 (31), 5615-5624CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)

    In this article, we investigated a series of organo-dyes, including methylene blue, fluorescein, Rhodamine 6G, Nile red and eosin Y, to perform a visible light-mediated controlled/"living" radical polymn. of methacrylates. We demonstrate that eosin Y and fluorescein were efficient catalysts to activate a photoinduced electron transfer-reversible addn.-fragmentation chain transfer (PET-RAFT) mechanism. The concn. of eosin Y was varied from 10 to 100 ppm with respect to monomers. This polymn. technique yielded well-defined (co)polymers with a good control of the mol. wts. ranging from 10 000 to 100 000 g mol-1 and low polydispersities (PDI < 1.30). A variety of functional monomers, including N,N-dimethylaminoethyl methacrylate, hydroxyl Et methacrylate, pentafluorophenyl methacrylate, glycidyl methacrylate, oligo(ethylene glycol) Me ether methacrylate (OEGMA), and methacrylic acid, were successfully polymd. Finally, the addn. of a tertiary amine, such as triethylamine, afforded the polymn. in the presence of air via a reductive quenching cycle. Different diblock polymethacrylate copolymers, i.e.PMMA-b-POEGMA and PMMA-b-PMMA, were prepd. to demonstrate the high end group fidelity.

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92. 92

    Shanmugam, S.; Xu, J.; Boyer, C. Chem. Sci. 2015, 6, 1341– 1349 DOI: 10.1039/C4SC03342F

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    92

    Utilizing the electron transfer mechanism of chlorophyll a under light for controlled radical polymerization

    Shanmugam, Sivaprakash; Xu, Jiangtao; Boyer, Cyrille

    Chemical Science (2015), 6 (2), 1341-1349CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)

    Efficient photoredox catalysts contg. transition metals, such as iridium and ruthenium, to initiate org. reactions and polymn. under visible light have recently emerged. However, these catalysts are composed of rare metals, which limit their applications. In this study, we report an efficient photoinduced living radical polymn. process that involves the use of chlorophyll as the photoredox biocatalyst. We demonstrate that chlorophyll a (the most abundant chlorophyll in plants) can activate a photoinduced electron transfer (PET) process that initiates a reversible addn.-fragmentation chain transfer (RAFT) polymn. under blue and red LED light (λmax = 461 and 635 nm, resp.). This process controls a wide range of functional and non-functional monomers, and offers excellent control over mol. wts. and polydispersities. The end group fidelity was demonstrated by NMR, UV-vis spectroscopy, and successful chain extensions for the prepn. of diblock copolymers.

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93. 93

    Okamoto, Y.; Habaue, S.; Isobe, Y. In Advances in Controlled/Living Radical Polymerization; American Chemical Society: Washington, D.C., 2003; Vol. 854, pp 59– 71.

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    High resolution NMR spectra of poly(N,N-dimethylacrylamide) in trichloromethane-d solution

    Huynh Ba Gia; McGrath, J. E.

    Polymer Bulletin (Berlin, Germany) (1980), 2 (12), 837-40CODEN: POBUDR; ISSN:0170-0839.

    High-resoln. NMR spectra of poly(N,N-dimethylacrylamide) [26793-34-0] indicated that anionic polymn. with sec-BuLi produces isotactic polymer [37165-17-6], whereas radical polymn. with AIBN gives mostly atactic polymer.

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    Habaue, S.; Isobe, Y.; Okamoto, Y. Tetrahedron 2002, 58, 8205– 8209 DOI: 10.1016/S0040-4020(02)00969-9

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    Yoshino, T.; Kikuchi, Y.; Komiyama, J. J. Phys. Chem. 1966, 70, 1059– 1063 DOI: 10.1021/j100876a017

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    Bulai, A.; Jimeno, M. L.; Alencar de Queiroz, A.-A.; Gallardo, A.; San Román, J. Macromolecules 1996, 29, 3240– 3246 DOI: 10.1021/ma951520v

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    Sugiyama, Y.; Satoh, K.; Kamigaito, M.; Okamoto, Y. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 2086– 2098 DOI: 10.1002/pola.21310

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    Iron-catalyzed radical polymerization of acrylamides in the presence of lewis acid for simultaneous control of molecular weight and tacticity

    Sugiyama, Yuya; Satoh, Kotaro; Kamigaito, Masami; Okamoto, Yoshio

    Journal of Polymer Science, Part A: Polymer Chemistry (2006), 44 (6), 2086-2098CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)

    This work is directed to the stereospecific living radical polymn. of acrylamides such as N,N-di-Me acrylamide (DMAM) and N-isopropylacrylamide (NIPAM) with an iron complex and a Lewis acid. DMAM was polymd. with [FeCp(CO)2]2 in conjunction with an alkyl iodide [(CH3)2C(CO2Et)I] as an initiator in the presence of Y(OTf)3 in toluene/methanol (1/1) at 60 °C to be converted almost quant. to the polymers with controlled mol. wts. and high isotacticity (m > 80%), wherein the Fe-complex generates radical species from a covalent C-I bond of the dormant species and the Lewis acid controls the stereochem. of the polymn. via coordination with the amide groups of the polymer terminal and the monomer. A series of Lewis acids were also used for the iron(I)-catalyzed DMAM polymn., and Yb(OTf)3 and Yb(NTf2)3 proved effective in giving isotactic polymers without deteriorating the mol. wt. control similar to Y(OTf)3. Furthermore, a slight enhancement of iso-specificity was obsd. for the iron-catalyzed system in comparison with the α,α-Azobisisobutyronitrile-initiated, when coupled with Y(OTf)3. Stereo-block polymn. of DMAM via a one-pot reaction was also achieved by just adding the Y(OTf)3 methanol soln. in the course of the polymn. to give atactic-b-isotactic poly(DMAM). A similar but slightly lower control in the mol. wt. and tacticity was achieved in the polymn. of NIPAM with [FeCp(CO)2]2/Y(OTf)3.

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     Ray, B.; Isobe, Y.; Morioka, K.; Habaue, S.; Okamoto, Y.; Kamigaito, M.; Sawamoto, M. Macromolecules 2003, 36, 543– 545 DOI: 10.1021/ma0257595

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     Murayama, H.; Satoh, K.; Kamigaito, M. In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP; American Chemical Society: Washington, D.C., 2009; Vol. 1024, pp 49– 63.

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     Radical coordination polymerization

     Kabanov, V. A.

     Journal of Polymer Science, Polymer Symposia (1980), 67 (Int. Symp. Macromol. Chem., IUPAC, 1978), 17-41CODEN: JPYCAQ; ISSN:0360-8905.

     The mechanism of homopolymn. of vinyl monomers in the presence of Lewis acid catalysts involves the usual addn. chain radical scheme and an initiation step with primary radical formation. A ternary donor-acceptor complex is formed when 2 monomers are present as in the copolymn. of Bu methacrylate [97-88-1] and 2,3-dimethylbutadiene [513-81-5] in the presence of Et2AlCl [96-10-6]. The ternary complex fulfills the monomer function in the chain-propagation reaction, and it can add to the propagating chain as an independent kinetic species to give alternating copolymers.

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     Luo, R.; Sen, A. Macromolecules 2007, 40, 154– 156 DOI: 10.1021/ma062341o

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     Isobe, Y.; Nakano, T.; Okamoto, Y. J. Polym. Sci., Part A: Polym. Chem. 2001, 39, 1463– 1471 DOI: 10.1002/pola.1123

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     Stereocontrol during the free-radical polymerization of methacrylates with Lewis acids

     Isobe, Yutaka; Nakano, Tamaki; Okamoto, Yoshio

     Journal of Polymer Science, Part A: Polymer Chemistry (2001), 39 (9), 1463-1471CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)

     The free-radical polymns. of Me methacrylate (MMA), Et methacrylate, iso-Pr methacrylate, and 2-methoxyethyl methacrylate were carried out in the presence of various Lewis acids. The MMA polymn. in the presence of scandium trifluoromethanesulfonate [Sc(OTf)3] in toluene or CHCl3 produced a polymer with a higher isotacticity and heterotacticity than that produced in the absence of Sc(OTf)3. Similar effects were obsd. during the polymn. of the other monomers. ScCl3, Yb(OTf)3, Er(OTf)3, HfCl4, HfBr4, and In(OTf)3 also increased the isotacticity and heterotacticity of the polymers. The effects of the Lewis acids were greater in a solvent with a lower polarity and were negligible in THF and N,N-dimethylformamide. Sc(OTf)3 was also found to accelerate the polymn. of MMA. On the basis of an NMR anal. of a mixt. of Sc(OTf)3, MMA, and poly(Me methacrylate), the monomer-Sc(OTf)3 interaction seems to be involved in the stereo-chem. mechanism of the polymn.

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106. 106

     Ray, B.; Isobe, Y.; Matsumoto, K.; Habaue, S.; Okamoto, Y.; Kamigaito, M.; Sawamoto, M. Macromolecules 2004, 37, 1702– 1710 DOI: 10.1021/ma035119h

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     Mueller, A. H. E.; Zhuang, R.; Yan, D.; Litvinenko, G. Macromolecules 1995, 28, 4326– 4333 DOI: 10.1021/ma00116a040

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     Goto, A.; Sato, K.; Tsujii, Y.; Fukuda, T.; Moad, G.; Rizzardo, E.; Thang, S. H. Macromolecules 2001, 34, 402– 408 DOI: 10.1021/ma0009451

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     Skrabania, K.; Miasnikova, A.; Bivigou-Koumba, A. M.; Zehm, D.; Laschewsky, A. Polym. Chem. 2011, 2, 2074– 2083 DOI: 10.1039/c1py00173f

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     109

     Examining the UV-vis absorption of RAFT chain transfer agents and their use for polymer analysis

     Skrabania, Katja; Miasnikova, Anna; Bivigou-Koumba, Achille Mayelle; Zehm, Daniel; Laschewsky, Andre

     Polymer Chemistry (2011), 2 (9), 2074-2083CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)

     The absorption characteristics of a large set of thiocarbonyl based chain transfer agents (CTAs) were studied by UV-vis spectroscopy in order to identify appropriate conditions for exploiting their absorbance bands in end-group anal. of polymers prepd. by reversible addn.-fragmentation chain transfer (RAFT) polymn. Substitution pattern and solvent polarity were found to affect notably the wavelengths and intensities of the π-π*- and n-π*-transition of the thiocarbonyl bond of dithioester and trithiocarbonate RAFT agents. Therefore, it is advisable to refer in end group anal. to the spectral parameters of low molar mass analogs of the active polymer chain ends, rather than to rely on the specific RAFT agent engaged in the polymn. When using appropriate conditions, the quantification of the thiocarbonyl end-groups via the π-π* band of the thiocarbonyl moiety around 300-310 nm allows a facile, sensitive and surprisingly precise estn. of the no. av. molar mass of the polymers produced, without the need of particular end group labels. Moreover, when addnl. methods for abs. molar mass detn. can be applied, the quantification of the thiocarbonyl end-groups by UV-spectroscopy provides a good est. of the degree of active end group for a given polymer sample.

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110. 110

     Chong, Y. K.; Moad, G.; Rizzardo, E.; Skidmore, M. A.; Thang, S. H. Macromolecules 2007, 40, 9262– 9271 DOI: 10.1021/ma071100t

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     There is no corresponding record for this reference.
111. 111

     Nuopponen, M.; Kalliomäki, K.; Laukkanen, A.; Hietala, S.; Tenhu, H. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 38– 46 DOI: 10.1002/pola.22355

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     111

     A-B-A stereoblock copolymers of N-isopropylacrylamide

     Nuopponen, Markus; Kalliomaki, Katriina; Laukkanen, Antti; Hietala, Sami; Tenhu, Heikki

     Journal of Polymer Science, Part A: Polymer Chemistry (2007), 46 (1), 38-46CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)

     A-B-A stereoblock polymers with atactic poly(N-isopropylacrylamide) (PNIPAM) as a hydrophilic block (either A or B) and a non-water-sol. block consisting of isotactic PNIPAM were synthesized using reversible addn. fragmentation chain transfer (RAFT) polymns. Yttrium trifluoromethanesulfonate was used in the tacticity control, and bifunctional S,S'-bis(α,α'-dimethyl-α''-acetic acid)-trithiocarbonate (BDAT) was utilized as a RAFT agent. Chain structures of the A-B-A stereoblock copolymers were detd. using 1H NMR, SEC, and MALDI-TOF mass spectrometry. BDAT proved to be an efficient RAFT agent in the controlled synthesis of stereoregular PNIPAM, and both atactic and isotactic PNIPAM were successfully used as macro RAFT agents. The glass transition temps. (Tg) of the resulting polymers were measured by differential scanning calorimetry. We found that the Tg of isotactic PNIPAM is mol. wt. dependent and varies in the present case between 115 and 158°. Stereoblock copolymers show only one Tg, indicating the miscibility of the blocks. Correspondingly, the Tg may be varied by varying the mutual lengths of the A and B blocks. The phase sepn. of aq. solns. upon increasing temp. is strongly affected by the isotactic blocks. At a fixed concn. (5 mg/mL), an increase of the isotacticity of the stereoblock copolymers decreases the demixing temp.

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112. 112

     Hietala, S.; Nuopponen, M.; Kalliomäki, K.; Tenhu, H. Macromolecules 2008, 41, 2627– 2631 DOI: 10.1021/ma702311a

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     There is no corresponding record for this reference.
113. 113

     Nuopponen, M.; Kalliomäki, K.; Aseyev, V.; Tenhu, H. Macromolecules 2008, 41, 4881– 4886 DOI: 10.1021/ma800083t

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     There is no corresponding record for this reference.
114. 114

     Shibata, T.; Satoh, K.; Kamigaito, M.; Okamoto, Y. J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 3609– 3615 DOI: 10.1002/pola.21469

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     114

     Simultaneous control of the stereospecificity and molecular weight in the ruthenium-catalyzed living radical polymerization of methyl and 2-hydroxyethyl methacrylates and sequential synthesis of stereoblock polymers

     Shibata, Takuya; Satoh, Kotaro; Kamigaito, Masami; Okamoto, Yoshio

     Journal of Polymer Science, Part A: Polymer Chemistry (2006), 44 (11), 3609-3615CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)

     The stereospecific living radical polymns. of Me methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) were achieved with a combination of ruthenium-catalyzed living radical and solvent-mediated stereospecific radical polymns. Among a series of ruthenium complexes [RuCl2(PPh3)3, Ru(Ind)Cl(PPh3)2, and RuCp*Cl(PPh3)2], Cp*-ruthenium afforded polymethyl methacrylate with highly controlled mol. wts. [wt. av. mol. wt./no. av. mol. wt. (Mw/Mn) = 1.08] and high syndiotacticity (r = 88%) in a fluoroalc. such as (CF3)2C(Ph)OH at 0°. On the other hand, a hydroxy-functionalized monomer, HEMA, was polymd. with RuCp*Cl(PPh3)2 in N,N-dimethylformamide and N,N-dimethylacetamide (DMA) to give syndiotactic polymers (r = 87-88%) with controlled mol. wts. (Mw/Mn = 1.12-1.16). This was the first example of the syndiospecific living radical polymn. of HEMA. A fluoroalc. [(CF3)2C(Ph)OH], which induced the syndiospecific radical polymn. of MMA, reduced the syndiospecificity in the HEMA polymn. to result in more or less atactic polymers (mm/mr/rr = 7.2/40.9/51.9%) with controlled mol. wts. in the presence of RuCp*Cl(PPh3)2 at 80°. A successive living radical polymn. of HEMA in two solvents, first DMA followed by (CF3)2C(Ph)OH, resulted in stereoblock poly(2-hydroxyethyl methacrylate) with syndiotactic-atactic segments.

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115. 115

     Zhao, Y.; Yu, M.; Zhang, S.; Wu, Z.; Liu, Y.; Peng, C.-H.; Fu, X. Chem. Sci. 2015, 6, 2979– 2988 DOI: 10.1039/C5SC00477B

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     115

     A well-defined, versatile photoinitiator (salen)Co-CO2CH3 for visible light-initiated living/controlled radical polymerization

     Zhao, Yaguang; Yu, Mengmeng; Zhang, Shuailin; Wu, Zhenqiang; Liu, Yuchu; Peng, Chi-How; Fu, Xuefeng

     Chemical Science (2015), 6 (5), 2979-2988CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)

     The control of the polymn. of a wide range of monomers under mild conditions by a single catalyst remains a major challenge in polymer science. We report a versatile, well-defined organocobalt salen complex to control living radical polymn. of different categories of monomers, including acrylates, acrylamides and vinyl acetate, under visible light irradn. at ambient temp. Both household light and sunlight were effectively applied in the synthesis of polymers with controlled mol. wts. and narrow polydispersities. Narrowly dispersed block copolymers (Mw/Mn < 1.2) were obtained under various conditions. The structures of the polymers were analyzed by 1H NMR, 12D NMR, 13C NMR, GPC, MALDI-TOF-MS and isotopic labeling expts., which showed that the ω and α ends of the polymer chains were capped with (salen)Co and -CO2CH3 segments, resp., from the photoinitiator (salen)Co-CO2CH3. The Ω end was easily functionalized through oxygen insertion followed by hydrolysis from 18O2 to -18OH. This robust system can proceed without any additives, and offers a versatile and green way to produce well-defined homo and block copolymers.

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116. 116

     Su, X.; Zhao, Z.; Li, H.; Li, X.; Wu, P.; Han, Z. Eur. Polym. J. 2008, 44, 1849– 1856 DOI: 10.1016/j.eurpolymj.2008.03.012

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     116

     Stereocontrol during photo-initiated controlled/living radical polymerization of acrylamide in the presence of Lewis acids

     Su, Xiaoli; Zhao, Zhengguo; Li, Hui; Li, Xinxin; Wu, Pingping; Han, Zhewen

     European Polymer Journal (2008), 44 (6), 1849-1856CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)

     Poly(acrylamide) (PAM) with controlled mol. wt. and tacticity was prepd. by UV-irradn.-initiated controlled/living radical polymn. in the presence of dibenzyl trithiocarbonate (DBTTC) and Y(OTf)3. The rapid and facile photo-initiated controlled/living polymn. at ambient temp. led to controlled mol. wt. and narrow polydispersity (M w /M n = 1.12-1.24) of PAM. The coordination of Y(OTf)3 with the last two amide groups in the growing chain radical effectively enhanced isotacticity of PAM. The isotactic sequence of dyads (m), triads (mm) and pentads (mmmm) in PAM were 70.32%, 50.95%, and 29.97%, resp., which were detd. by the resonance of methine (CH) groups in PAM under 13C NMR expt. Factors affecting stereocontrol during the polymn. were studied, including the type of Lewis acids, concn. of Y(OTf)3, and monomer conversion. It is intriguing that the meso tacticity increased gradually with chain propagation and quite higher isotacticity (m = 93.01%, mm = 86.57%) was obtained in the later polymn. stage (conversion 65-85%).

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117. 117

     Ishitake, K.; Satoh, K.; Kamigaito, M.; Okamoto, Y. Polym. Chem. 2012, 3, 1750– 1757 DOI: 10.1039/C1PY00401H

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     117

     From-syndiotactic-to-isotactic stereogradient methacrylic polymers by RAFT copolymerization of methacrylic acid and its bulky esters

     Ishitake, Kenji; Satoh, Kotaro; Kamigaito, Masami; Okamoto, Yoshio

     Polymer Chemistry (2012), 3 (7), 1750-1757CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)

     The synthesis of stereogradient polymers with tacticities that vary from predominantly syndiotactic to highly isotactic was investigated by reversible addn.-fragmentation chain transfer (RAFT) copolymn. of bulky methacrylates, such as triphenylmethyl methacrylate (TrMA) and 1-phenyldibenzosuberyl methacrylate (PDBSMA) and methacrylic acid (MAA) in both non-polar and polar solvents. The MAA monomer showed increased reactivity in toluene because of hydrogen bonding and was consumed slightly faster than TrMA or PDBSMA. However, the RAFT copolymn. of TrMA and MAA in 1,4-dioxane resulted in consumption of both monomers at the same rate. The copolymers can be easily converted to homopoly(MAA) by the acid hydrolysis of the bulky group and converted further to poly(Me methacrylate) by Me esterification using trimethylsilyldiazomethane to analyze the mol. wts. and tacticity. The mol. wts. of the polymers obtained in both solvents increased with monomer conversion, which indicates that controlled/living radical copolymn. proceeded irresp. of the solvents. 13C NMR analyses of the polymers revealed that stereogradient polymers were produced in toluene, in which the tacticity changed from mm = 11% to nearly 100%, whereas the copolymers obtained in 1,4-dioxane resulted in nearly atactic enchainment (rr/mr/mm ≈ 38/49/13), independent of monomer conversion. A similar stereogradient copolymer was also obtained by RAFT copolymn. of PDBSMA and MAA in toluene, where the isotacticity changed more gradually from mm = 14% to nearly 100%.

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