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Journal articles on the topic 'Atom Transfer Radical Polymerization Techniques'

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Published: 7 September 2023

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1

Fantin, Marco, Francesca Lorandi, Armando Gennaro, Abdirisak Isse, and Krzysztof Matyjaszewski. "Electron Transfer Reactions in Atom Transfer Radical Polymerization." Synthesis 49, no. 15 (July 4, 2017): 3311–22. http://dx.doi.org/10.1055/s-0036-1588873.

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Electrochemistry may seem an outsider to the field of polymer science and controlled radical polymerization. Nevertheless, several electrochemical methods have been used to determine the mechanism of atom transfer radical polymerization (ATRP), using both a thermodynamic and a kinetic approach. Indeed, electron transfer reactions involving the metal catalyst, initiator/dormant species, and propagating radicals play a crucial role in ATRP. In this mini-review, electrochemical properties of ATRP catalysts and initiators are discussed, together with the mechanism of the atom and electron transfer in ATRP.1 Introduction2 Thermodynamic and Electrochemical Properties of ATRP Catalysts3 Thermodynamic and Electrochemical Properties of Alkyl Halides and Alkyl Radicals4 Atom Transfer from an Electrochemical and Thermodynamic Standpoint5 Mechanism of Electron Transfer in ATRP6 Electroanalytical Techniques for the Kinetics of ATRP Activation7 Electrochemically Mediated ATRP8 Conclusions

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2

Kajiwara, Atsushi. "Characterizations of radicals formed in radical polymerizations and transfer reactions by electron spin resonance spectroscopy." Pure and Applied Chemistry 90, no. 8 (August 28, 2018): 1237–54. http://dx.doi.org/10.1515/pac-2018-0401.

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Abstract Electron spin resonance (ESR, aka electron paramagnetic resonance, EPR) investigations have been conducted on radicals formed during radical polymerizations and provide a detailed characterization of the active radical species. Active propagating radicals can be observed during actual radical polymerizations by ESR/EPR. The chain lengths of the observed radicals were estimated by a combination of atom transfer radical polymerization (ATRP) and ESR/EPR. The structures of the chain end radicals were determined by analysis of the ESR/EPR spectra. An increase in the dihedral angles between terminal p-orbital of radical and Cβ–H bonds was observed with increasing chain lengths of methacrylate polymers. Radical transfer reactions were observed during radical polymerization of acrylates. A combination of ATRP and ESR/EPR clarified a 1,5-hydrogen shift mechanism of the radical transfer reactions using model adamantyl acrylate radicals. Penultimate unit effects were also observed. Time-resolved ESR/EPR (TR ESR) spectroscopy clarified the initiation processes of an alternating copolymerization of styrene with maleic anhydride and the copolymerization of styrene with 1,3-butadiene. Several unsolved problems in conventional radical polymerization processes have been clarified using combinations of ATRP with ESR/EPR and TR ESR. Characterization of the radicals in radical polymerizations using various ESR techniques would definitely provide interesting and useful information on conventional radical polymerizations.

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3

Dadashi-Silab, Sajjad, and Krzysztof Matyjaszewski. "Iron Catalysts in Atom Transfer Radical Polymerization." Molecules 25, no. 7 (April 3, 2020): 1648. http://dx.doi.org/10.3390/molecules25071648.

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Catalysts are essential for mediating a controlled polymerization in atom transfer radical polymerization (ATRP). Copper-based catalysts are widely explored in ATRP and are highly efficient, leading to well-controlled polymerization of a variety of functional monomers. In addition to copper, iron-based complexes offer new opportunities in ATRP catalysis to develop environmentally friendly, less toxic, inexpensive, and abundant catalytic systems. Despite the high efficiency of iron catalysts in controlling polymerization of various monomers including methacrylates and styrene, ATRP of acrylate-based monomers by iron catalysts still remains a challenge. In this paper, we review the fundamentals and recent advances of iron-catalyzed ATRP focusing on development of ligands, catalyst design, and techniques used for iron catalysis in ATRP.

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4

Lowe, A. B., and C. L. McCormick. "Homogeneous Controlled Free Radical Polymerization in Aqueous Media." Australian Journal of Chemistry 55, no. 7 (2002): 367. http://dx.doi.org/10.1071/ch02053.

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The ability to conduct controlled radical polymerizations (CRP) in homogeneous aqueous media is discussed. Three main techniques, namely stable free radical polymerization (SFRP), with an emphasis on nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT) are examined. No examples exist of homogeneous aqueous NMP polymerization, but mixed water/solvent systems are discussed with specific reference to the NMP of sodium 4-styrenesulfonate. Aqueous ATRP is possible, although monomer choice is limited to methacrylates and certain styrenics. Finally, homogeneous aqueous RAFT polymerizations are examined. We demonstrate the greater versatility of this technique, at least in terms of monomer variety, by discussing the controlled polymerization of charged and neutral acrylamido monomers and of a series of ionic styrenic monomers. Many of these monomers cannot/have not been polymerized by either NMP or ATRP.

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5

Yuan, Ming, Xuetao Cui, Wenxian Zhu, and Huadong Tang. "Development of Environmentally Friendly Atom Transfer Radical Polymerization." Polymers 12, no. 9 (August 31, 2020): 1987. http://dx.doi.org/10.3390/polym12091987.

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Atom transfer radical polymerization (ATRP) is one of the most successful techniques for the preparation of well-defined polymers with controllable molecular weights, narrow molecular weight distributions, specific macromolecular architectures, and precisely designed functionalities. ATRP usually involves transition-metal complex as catalyst. As the most commonly used copper complex catalyst is usually biologically toxic and environmentally unsafe, considerable interest has been focused on iron complex, enzyme, and metal-free catalysts owing to their low toxicity, inexpensive cost, commercial availability and environmental friendliness. This review aims to provide a comprehensive understanding of iron catalyst used in normal, reverse, AGET, ICAR, GAMA, and SARA ATRP, enzyme as well as metal-free catalyst mediated ATRP in the point of view of catalytic activity, initiation efficiency, and polymerization controllability. The principle of ATRP and the development of iron ligand are briefly discussed. The recent development of enzyme-mediated ATRP, the latest research progress on metal-free ATRP, and the application of metal-free ATRP in interdisciplinary areas are highlighted in sections. The prospects and challenges of these three ATRP techniques are also described in the review.

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6

Min, Ke, and Krzysztof Matyjaszewski. "Atom transfer radical polymerization in aqueous dispersed media." Open Chemistry 7, no. 4 (December 1, 2009): 657–74. http://dx.doi.org/10.2478/s11532-009-0092-1.

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AbstractDuring the last decade, atom transfer radical polymerization (ATRP) received significant attention due to its exceptional capability of synthesizing polymers with pre-determined molecular weight, well-defined molecular architectures and various functionalities. It is economically and environmentally attractive to adopt ATRP to aqueous dispersed media, although the process is challenging. This review summarizes recent developments of conducting ATRP in aqueous dispersed media. The issues related to retaining “controlled/living” character as well as colloidal stability during the polymerization have to be considered. Better understanding the ATRP mechanism and development of new initiation techniques, such as activators generated by electron transfer (AGET) significantly facilitated ATRP in aqueous systems. This review covers the most important progress of ATRP in dispersed media from 1998 to 2009, including miniemulsion, microemulsion, emulsion, suspension and dispersed polymerization.

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7

Li, Song Tao, Dan Li, and Chun Ju He. "Synthesis of Allyl Functionalized Telechelic PVP by Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization." Materials Science Forum 789 (April 2014): 235–39. http://dx.doi.org/10.4028/www.scientific.net/msf.789.235.

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Telechelic polymers have been explored widely because they are precursors for preparing multi-block copolymers, grafted polymers, star polymers, and polymer networks [1-2]. A variety of telechelic polymers with terminals like hydroxy, carboxylic, epoxy groups and carbon–carbon double bond have been prepared by controlled radical polymerization (CRP) techniques including nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT)[3-5].The CRP techniques can not only control the molecular weight but also can be carried out in the presence of many functional groups from monomers, initiators, or chain transfer agents (CTA).

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8

Davis, Kelly A., and Krzysztof Matyjaszewski. "ABC Triblock Copolymers Prepared Using Atom Transfer Radical Polymerization Techniques." Macromolecules 34, no. 7 (March 2001): 2101–7. http://dx.doi.org/10.1021/ma002050u.

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9

Lacroix-Desmazes, Patrick, Bruno Améduri, and Bernard Boutevin. "Use of Fluorinated Organic Compounds in Living Radical Polymerizations." Collection of Czechoslovak Chemical Communications 67, no. 10 (2002): 1383–415. http://dx.doi.org/10.1135/cccc20021383.

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Controlled/living radical polymerization (LRP) is a field of special interest because it allows tailoring well-defined macromolecular architectures such as telechelic, block, graft or star copolymers. Since the eighties, several techniques have been reported [such as the iniferter method, nitroxide-mediated radical polymerization (NMP), atom transfer radical polymerization (ATRP), iodine transfer polymerization (ITP), and reversible addition-fragmentation chain transfer (RAFT)] giving rise to a huge number of publications and patents. This review aims at illustrating the contribution of fluorinated organic compounds in this area of research through the use of fluorinated initiators (dithiocarbamates, xanthates, tetraphenylethanes, alkoxyamines, fluorinated alkyl halides, and dithioesters) or other fluorinated molecules (ligands, solvents). Another point depicts the LRP of various fluorinated monomers (methacrylates, acrylates, styrenics, and alkenes). Finally, fluorinated block and graft copolymers prepared by LRP have been reported. A review with 165 references.

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10

O'Donnell, Patrick M., and Kenneth B. Wagener. "Graft copolymers by acyclic diene metathesis and atom transfer radical polymerization techniques." Journal of Polymer Science Part A: Polymer Chemistry 41, no. 18 (August 4, 2003): 2816–27. http://dx.doi.org/10.1002/pola.10852.

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11

Zhang, Xiu Mei, Jian Feng Ji, Yan Jun Tang, and Yu Zhao. "Wood Pulp Fibers Grafted with Polyacrylamide through Atom Transfer Radical Polymerization." Advanced Materials Research 396-398 (November 2011): 1458–61. http://dx.doi.org/10.4028/www.scientific.net/amr.396-398.1458.

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Bleached wood pulp fibers grafted with polyacrylamide (PAM) was synthesized through surface-initiated atom transfer radical polymerization (SI-ATRP) to be applied in papermaking. The ATRP macroinitiator was prepared by esterification of hydroxyl groups of wood fibers with α-bromoisobutyryl bromide (α-BIBB). The bromine atoms on the surface of the macroinitiator were characterized and calculated by FT-IR, EDXS and TGA techniques. The ATRP grafting reaction conditions of fiber-PMA were discussed and determined. To optimize the polymerization in the CuBr/PMDETA catalytic system, several influencing factors on grafting yield were investigated, including solvent, reaction temperature, monomer concentration and sacrificial initiator. The PAM grafted fibers were characterized by FT-IR and TGA analyses.

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12

OHOKA, Masataka, Junpei KUNO, Katsuhiro YAMASHITA, Hideo OHKITA, Shinzaburo ITO, Yoshinobu TSUJII, and Takeshi FUKUDA. "Living Polymerization of Photofunctional Carbazole Polymers by Atom Transfer Radical Polymerization Technique." KOBUNSHI RONBUNSHU 59, no. 7 (2002): 421–26. http://dx.doi.org/10.1295/koron.59.421.

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13

Chan-Seng, Delphine, and Michael K. Georges. "Living radical emulsion polymerization using the nanoprecipitation technique: An extension to atom transfer radical polymerization." Journal of Polymer Science Part A: Polymer Chemistry 44, no. 13 (2006): 4027–38. http://dx.doi.org/10.1002/pola.21506.

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14

Agudelo, Natalia A., Andrea M. Elsen, Hongkun He, Betty L. López, and Krzysztof Matyjaszewski. "ABA triblock copolymers from two mechanistic techniques: Polycondensation and atom transfer radical polymerization." Journal of Polymer Science Part A: Polymer Chemistry 53, no. 2 (July 9, 2014): 228–38. http://dx.doi.org/10.1002/pola.27300.

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15

Hussain, Hazrat, Elkin Amado, and Jörg Kressler. "Functional Polyether-based Amphiphilic Block Copolymers Synthesized by Atom-transfer Radical Polymerization." Australian Journal of Chemistry 64, no. 9 (2011): 1183. http://dx.doi.org/10.1071/ch11147.

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This review deals with the synthesis, physical properties, and applications of amphiphilic block copolymers based on hydrophilic poly(ethylene oxide) (PEO) or hydrophobic poly(propylene oxide) (PPO). Oligomeric PEO and PPO are frequently functionalized by converting their OH end groups into macroinitiators for atom-transfer radical polymerization. They are then used to generate additional blocks as part of complex copolymer architectures. Adding hydrophobic and hydrophilic blocks, respectively, leads to polymers with amphiphilic character in water. They are surface active and form micelles above a critical micellization concentration. Together with recent developments in post-polymerization techniques through quantitative coupling reactions (‘click’ chemistry) a broad variety of tailored functionalities can be introduced to the amphiphilic block copolymers. Examples are outlined including stimuli responsiveness, membrane penetrating ability, formation of multi-compartmentalized micelles, etc.

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16

Sathesh, Venkatesan, Jem-Kun Chen, Chi-Jung Chang, Junko Aimi, Zong-Cheng Chen, Yu-Chih Hsu, Yi-Shen Huang, and Chih-Feng Huang. "Synthesis of Poly(ε-caprolactone)-Based Miktoarm Star Copolymers through ROP, SA ATRC, and ATRP." Polymers 10, no. 8 (August 2, 2018): 858. http://dx.doi.org/10.3390/polym10080858.

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The synthesis of novel branched/star copolymers which possess unique physical properties is highly desirable. Herein, a novel strategy was demonstrated to synthesize poly(ε-caprolactone) (PCL) based miktoarm star (μ-star) copolymers by combining ring-opening polymerization (ROP), styrenics-assisted atom transfer radical coupling (SA ATRC), and atom transfer radical polymerization (ATRP). From the analyses of gel permeation chromatography (GPC), proton nuclear magnetic resonance (1H NMR), and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), well-defined PCL-μ-PSt (PSt: polystyrene), and PCL-μ-PtBA (PtBA: poly(tert-butyl acrylate) μ-star copolymers were successfully obtained. By using atomic force microscopy (AFM), interestingly, our preliminary examinations of the μ-star copolymers showed a spherical structure with diameters of ca. 250 and 45 nm, respectively. We successfully employed combinations of synthetic techniques including ROP, SA ATRC, and ATRP with high effectiveness to synthesize PCL-based μ-star copolymers.

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17

Lu, Chuanwei, Chunpeng Wang, Juan Yu, Jifu Wang, and Fuxiang Chu. "Metal-free ATRP “grafting from” technique for renewable cellulose graft copolymers." Green Chemistry 21, no. 10 (2019): 2759–70. http://dx.doi.org/10.1039/c9gc00138g.

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Photoinduced metal-free “grafting from” atom transfer radical polymerization (ATRP) has been successfully applied to the fabrication of renewable cellulose graft copolymers with the aid of 2-bromo-2-phenylacetyl ester-modified ethyl cellulose as the macroinitiator.

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18

Kwark, Young-Je. "Preparation of branched polystyrene using atom transfer radical polymerization techniques and protection-deprotection chemistry." Macromolecular Research 16, no. 3 (April 2008): 238–46. http://dx.doi.org/10.1007/bf03218859.

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19

Yhaya, Firdaus, Andrew M. Gregory, and Martina H. Stenzel. "Polymers with Sugar Buckets - The Attachment of Cyclodextrins onto Polymer Chains." Australian Journal of Chemistry 63, no. 2 (2010): 195. http://dx.doi.org/10.1071/ch09516.

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This Review summarizes the structures obtained when marrying synthetic polymers of varying architectures with cyclodextrins. Polymers with cyclodextrin pendant groups were obtained by directly polymerizing cyclodextrin-based monomers or by postmodification of reactive polymers with cyclodextrins. Star polymers with cyclodextrin as the core with up to 21 arms were usually obtained by using modified cyclodextrins as initiator or controlling agent. Limited reports are available on the synthesis of star polymers by arm-first techniques, which all employed azide-functionalized cyclodextrin and ‘click’ chemistry to attach seven polymer arms to the cyclodextrin core. Polymer chains with one or two cyclodextrin terminal units were reported as well as star polymers carrying a cyclodextrin molecule at the end of each arm. Cyclodextrin polymers were obtained using different polymerization techniques ranging from atom transfer radical polymerization, reversible addition–fragmentation chain transfer polymerization, nitroxide-mediated polymerization, free radical polymerization to (ionic) ring-opening polymerization, and polycondensation. Cyclodextrin polymers touch all areas of polymer science from gene delivery, self-assembled structures, drug carriers, molecular sensors, hydrogels, and liquid crystalline polymers. This Review attempts to focus on the range of work conducted with polymers and cyclodextrins and highlights some of the key areas where these macromolecules have been applied.

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20

Słowikowska, Monika, Kamila Chajec, Adam Michalski, Szczepan Zapotoczny, and Karol Wolski. "Surface-Initiated Photoinduced Iron-Catalyzed Atom Transfer Radical Polymerization with ppm Concentration of FeBr3 under Visible Light." Materials 13, no. 22 (November 14, 2020): 5139. http://dx.doi.org/10.3390/ma13225139.

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Reversible deactivation radical polymerizations with reduced amount of organometallic catalyst are currently a field of interest of many applications. One of the very promising techniques is photoinduced atom transfer radical polymerization (photo-ATRP) that is mainly studied for copper catalysts in the solution. Recently, advantageous iron-catalyzed photo-ATRP (photo-Fe-ATRP) compatible with high demanding biological applications was presented. In response to that, we developed surface-initiated photo-Fe-ATRP (SI-photo-Fe-ATRP) that was used for facile synthesis of poly(methyl methacrylate) brushes with the presence of only 200 ppm of FeBr3/tetrabutylammonium bromide catalyst (FeBr3/TBABr) under visible light irradiation (wavelength: 450 nm). The kinetics of both SI-photo-Fe-ATRP and photo-Fe-ATRP in solution were compared and followed by 1H NMR, atomic force microscopy (AFM) and gel permeation chromatography (GPC). Brush grafting densities were determined using two methodologies. The influence of the sacrificial initiator on the kinetics of brush growth was studied. It was found that SI-photo-Fe-ATRP could be effectively controlled even without any sacrificial initiators thanks to in situ production of ATRP initiator in solution as a result of reaction between the monomer and Br radicals generated in photoreduction of FeBr3/TBABr. The optimized and simplified reaction setup allowed synthesis of very thick (up to 110 nm) PMMA brushes at room temperature, under visible light with only 200 ppm of iron-based catalyst. The same reaction conditions, but with the presence of sacrificial initiator, enabled formation of much thinner layers (18 nm).

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21

Fristrup, Charlotte Juel, Katja Jankova, and Søren Hvilsted. "Surface-initiated atom transfer radical polymerization—a technique to develop biofunctional coatings." Soft Matter 5, no. 23 (2009): 4623. http://dx.doi.org/10.1039/b821815c.

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22

Zhai, Maolin, Jinhua Chen, Shin Hasegawa, and Yasunari Maekawa. "Synthesis of fluorinated polymer electrolyte membranes by radiation grafting and atom transfer radical polymerization techniques." Polymer 50, no. 5 (February 2009): 1159–65. http://dx.doi.org/10.1016/j.polymer.2009.01.014.

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23

Kajiwara, Atsushi. "A combination of Electron Spin Resonance spectroscopy/atom transfer radical polymerization (ESR/ATRP) techniques for fundamental investigation of radical polymerizations of (meth)acrylates." Polymer 72 (August 2015): 253–63. http://dx.doi.org/10.1016/j.polymer.2015.04.006.

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24

McDonald, Kyle A., Jeremy I. Feldblyum, Kyoungmoo Koh, Antek G. Wong-Foy, and Adam J. Matzger. "Polymer@MOF@MOF: “grafting from” atom transfer radical polymerization for the synthesis of hybrid porous solids." Chemical Communications 51, no. 60 (2015): 11994–96. http://dx.doi.org/10.1039/c5cc03027g.

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PMMA@IRMOF-3@MOF-5, a hybrid polymer–MOF composite, was produced through a combination of core–shell and post-synthetic modification techniques. The core–shell architecture allows polymer chains to be tethered to the outer shell selectively.

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25

Deoghare, Chetana Anand. "Thermally Stable Copolymers with Pendant “N-Arylimide” Groups Via Reversible Deactivation Radical Polymerization Technique." ECS Transactions 107, no. 1 (April 24, 2022): 18175–87. http://dx.doi.org/10.1149/10701.18175ecst.

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This paper reports the synthesis of copolymers of N-arylitaconimides (NAI) and methyl methacrylate (MMA) with random architecture via activator generated electron transfer atom transfer radical polymerization (AGET-ATRP) method, resulting in N-arylimide as pendant group.The AGET-ATRP is a versatile and famous reversible deactivation radical polymerization technique used to synthesize the well defined polymers. The structural characterizations of obtained copolymers were done using FT-IR, 1H-NMR spectroscopy and elemental analysis. The molecular weights of copolymers were in the range 8,000-20,000 g/ mol with a narrow polydispersity index i.e. 1.2-1.3. Thermal characterization of Poly(NAI-ran-MMA) copolymers were done using differential scanning calorimetry (DSC) and thermogravimetric analysis (TG/ DTG). DSC scans show 60-117% enhancements in the glass transition temperature (Tg), as compared to Poly(methyl methacrylate). The rate of copolymerization, molecular weight and Tg were observed to increase with increase in electron releasing nature of the substituent on aromatic ring of the pendant group.

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26

Holmberg, Svante, Peter Holmlund, Carl-Eric Wilén, Tanja Kallio, Göran Sundholm, and Franciska Sundholm. "Synthesis of proton-conducting membranes by the utilization of preirradiation grafting and atom transfer radical polymerization techniques." Journal of Polymer Science Part A: Polymer Chemistry 40, no. 4 (January 4, 2002): 591–600. http://dx.doi.org/10.1002/pola.10146.

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27

Asl ah A kses and S leyman Sara, Asl ah A. kses and S. leyman Sara. "Characterization and Synthesis of This Comb Type Copolymer with Styrene Using A Macromonomer Containing Polyethylmethacrylate." Journal of the chemical society of pakistan 41, no. 4 (2019): 569. http://dx.doi.org/10.52568/000775/jcsp/41.04.2019.

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In this study, firstly 7-hydroxy-4-chloromethyl coumarin (CMHC) was synthesized from reaction of ethyl 4-chloroacetoasetate with resorcinol. Then, the poly(ethyl methacrylate) coumarin end grouped having hydroxyl (CEMA) was prepared by ethyl methacrylate with using (CMHC) as initiator by atom transfer radical polymerization (ATRP) method. A macromonomer (CMEMA) was synthesized from reaction of methacryloyl chloride and poly(EMA) ended coumarin having OH group (CEMA). Molecular brush of P(CMEMA-comb-%16St) was synthesized by reaction of macromonomer CMEMA and styrene by free radical polymerization method (SRP). The structures of the prepared macromonomer and molecular brush were characterized by FT-IR and 1H-NMR techniques. The thermal behavior of P(CMEMA-comb-%St) has been investigated by TGA, and the glass transition temperatures have been measured on DSC. The average molecular weights and polydispersity were determined by GPC. The dielectric behavior of P(CMEMA-comb-%16St) was investigated as a function of temperature and frequency. The intrinsic viscosity [] of P(CMEMA-comb-%16St) was determinated.

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28

Sasai, Yasushi, Michinori Oikawa, Shin-ichi Kondo, and Masayuki Kuzuya. "Surface Engineering of Polymer Sheet by Plasma Techniques and Atom Transfer Radical Polymerization for Covalent Immobilization of Biomolecules." Journal of Photopolymer Science and Technology 2, no. 2 (2007): 197–200. http://dx.doi.org/10.2494/photopolymer.2.197.

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29

Sasai, Yasushi, Michinori Oikawa, Shin-ichi Kondo, and Masayuki Kuzuya. "Surface Engineering of Polymer Sheet by Plasma Techniques and Atom Transfer Radical Polymerization for Covalent Immobilization of Biomolecules." Journal of Photopolymer Science and Technology 20, no. 2 (2007): 197–200. http://dx.doi.org/10.2494/photopolymer.20.197.

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30

Mouanda, Brigitte, Esmeless Bassa, Guy Deniau, Pascale Jegou, Pascal Viel, and Serge Palacin. "Comparison of two “grafting from” techniques for surface functionalization: Cathodic electrografting and surface-initiated atom transfer radical polymerization." Journal of Electroanalytical Chemistry 629, no. 1-2 (April 2009): 102–9. http://dx.doi.org/10.1016/j.jelechem.2009.02.003.

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31

Xu, Jian Feng, Xiao Quan Peng, and Chun Ju He. "A Novel Method for the Synthesis of Amphiphilic Copolymer: PHEMA-b-PDMS-b-PHEMA." Materials Science Forum 789 (April 2014): 230–34. http://dx.doi.org/10.4028/www.scientific.net/msf.789.230.

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In this study, a novel amphiphilic copolymer based on the flexible polydimethylsiloxane (PDMS) macroinitiator was successfully prepared by atom transfer radical polymerization (ATRP). First, the high molecular weight bis (hydroxyalkyl)-terminated PDMS was prepared by hydrosilation reaction between hydrogen-terminated PDMS and 2-allyloxyethanol in the presence of Karstedt’s catalyst. The macroinitiator Br-PDMS-Br was prepared by the reaction between different molecular weight bis (hydroxyalkyl)-terminated PDMS and 2-bromoisobutyry bromide. Then the amphiphilic ABA-type block copolymers of poly [dimethylsiloxane-b-(hydroxylethyl methacrylate)] were initiated by bromide end-capped PDMS with HEMA, under an appropriate catalyst/ligand system of CuCl/bpy. The polymerization proceeded with first-order kinetics. It showed that the reaction system was a controlled/‘living’ polymerization. The triblock copolymers were characterized by FTIR, 1H-NMR, TGA and GPC techniques. GPC results showed the tribolck copolymer had narrow polydispersity of Mw/Mn (PDI<1.5). TGA results showed the good thermal stability of the triblock copolymer.

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32

Chan-Seng, Delphine, David A. Rider, Gérald Guérin, and Michael K. Georges. "Block copolymer preparation by atom transfer radical polymerization under emulsion conditions using a nanoprecipitation technique." Journal of Polymer Science Part A: Polymer Chemistry 46, no. 2 (January 15, 2008): 625–35. http://dx.doi.org/10.1002/pola.22410.

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33

Surmacz, Karolina, Paweł Błoniarz, and Paweł Chmielarz. "Coffee Beverage: A New Strategy for the Synthesis of Polymethacrylates via ATRP." Molecules 27, no. 3 (January 27, 2022): 840. http://dx.doi.org/10.3390/molecules27030840.

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Coffee, the most popular beverage in the 21st century society, was tested as a reaction environment for activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) without an additional reducing agent. Two blends were selected: pure Arabica beans and a proportional blend of Arabica and Robusta beans. The use of the solution received from the mixture with Robusta obtained a high molecular weight polymer product in a short time while maintaining a controlled structure of the synthesized product. Various monomers with hydrophilic characteristics, i.e., 2-(dimethylamino)ethyl methacrylate (DMAEMA), oligo(ethylene glycol) methyl ether methacrylate (OEGMA500), and glycidyl methacrylate (GMA), were polymerized. The proposed concept was carried out at different concentrations of coffee grounds, followed by the determination of the molar concentration of caffeine in applied beverages using DPV and HPLC techniques.

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34

Klaysri, Rachan, Sopita Wichaidit, Piyasan Praserthdam, and Okorn Mekasuwandumrong. "Grafting of TiO₂ on PMMA Film and Reusability in Photodegradation of Organic Dye." Advances in Science and Technology 99 (October 2016): 17–21. http://dx.doi.org/10.4028/www.scientific.net/ast.99.17.

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Grafting TiO2 on PMMA was studied by atom-transfer radical-polymerization (ATRP). Each step in grafting process was monitored by fourier transform infrared spectroscopy (FT-IR), 1H NMR and 13C NMR spectra. The glass temperature of grafted-PMMA film was determined by using differential scanning calorimetry (DSC). The morphology and bulk composition were characterized by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX). The surface composition was characterized by X-ray photoelectron spectroscopy (XPS). As results, a novel method of grafting TiO2 on PMMA was successfully grafted and confirmed in various techniques. The photocatlytic activity was evaluated under UV and visible light irradiation. The reusability of TiO2-g-PMMA films was studied in details.

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35

Ejaz, Muhammad, Shinpei Yamamoto, Kohji Ohno, Yoshinobu Tsujii, and Takeshi Fukuda. "Controlled Graft Polymerization of Methyl Methacrylate on Silicon Substrate by the Combined Use of the Langmuir−Blodgett and Atom Transfer Radical Polymerization Techniques." Macromolecules 31, no. 17 (August 1998): 5934–36. http://dx.doi.org/10.1021/ma980240n.

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36

Gautam, Bhaskarchand, and Hsiao-hua Yu. "Self-Cleaning Cotton Obtained after Grafting Thermoresponsive Poly(N-vinylcaprolactam) through Surface-Initiated Atom Transfer Radical Polymerization." Polymers 12, no. 12 (December 5, 2020): 2920. http://dx.doi.org/10.3390/polym12122920.

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Although the performance of smart textiles would be enhanced if they could display self-cleaning ability toward various kinds of contamination, the procedures that have been used previously to impart the self-cleaning potential to these functional fabrics (solvent casting, dip coating, spin coating, surface crosslinking) have typically been expensive and/or limited by uncontrollable polymer thicknesses and morphologies. In this paper, we demonstrate the use of atomic transfer radical polymerization for the surface-initiated grafting of poly(N-vinylcaprolactam), a thermoresponsive polymer, onto cotton. We confirmed the thermoresponsiveness and reusability of the resulting fabric through water contact angle measurements and various surface characterization techniques (scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy). Finally, we validated the self-cleaning performance of the fabric by washing away an immobilized fluorescent protein in deionized water under thermal stimulus. Fluorescence micrographs revealed that, after the fifth wash cycle, the fabric surface had undergone efficient self-cleaning of the stain, making it an effective self-cleaning material. This approach appears to have potential for application in the fields of smart textiles, responsive substrates, and functional fabrics.

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37

Aswale, Suraj, Minji Kim, Dongwoo Kim, Aruna Kumar Mohanty, Heung Bae Jeon, Hong Y. Cho, and Hyun-jong Paik. "Synthesis and Characterization of Spirocyclic Mid-Block Containing Triblock Copolymer." Polymers 15, no. 7 (March 28, 2023): 1677. http://dx.doi.org/10.3390/polym15071677.

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Polymers containing cyclic derivatives are a new class of macromolecular topologies with unique properties. Herein, we report the synthesis of a triblock copolymer containing a spirocyclic mid-block. To achieve this, a spirocyclic polystyrene (cPS) mid-block was first synthesized by atom transfer radical polymerization (ATRP) using a tetra-functional initiator, followed by end-group azidation and a copper (I)-catalyzed azide-alkyne cycloaddition reaction. The resulting functional cPS was purified using liquid chromatography techniques. Following the esterification of cPS, a macro-ATRP initiator was obtained and used to synthesize a poly (methyl methacrylate)-block-cPS-block-poly (methyl methacrylate) (PMMA-b-cPS-b-PMMA) triblock copolymer. This work provides a synthetic strategy for the preparation of a spirocyclic macroinitiator for the ATRP technique and as well as liquid chromatographic techniques for the purification of (spiro) cyclic polymers.

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38

Yang, Wenming, Lukuan Liu, Zhiping Zhou, Hong Liu, Binze Xie, and Wanzhen Xu. "Rational preparation of dibenzothiophene-imprinted polymers by surface imprinting technique combined with atom transfer radical polymerization." Applied Surface Science 282 (October 2013): 809–19. http://dx.doi.org/10.1016/j.apsusc.2013.06.063.

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39

Shi, Shu Xian, Jian Liu, Yu Zheng Xia, Shu Ke Jiao, and Xiao Yu Li. "Synthesis of Novel Amphiphilic Block Copolymers of Poly-N-vinylpyrrolidone and Poly (D, L-lactide) by Atom Transfer Radical Polymerization." Advanced Materials Research 11-12 (February 2006): 461–64. http://dx.doi.org/10.4028/www.scientific.net/amr.11-12.461.

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In order to improve the hydrophilicity of poly (D,L-latide) (PDLLA), a novel amphiphilic ABA-type triblock copolymers of poly-N-vinylpyrrolidone (A) and poly (D, L-lactide) (B), were successfully synthesized by atom transfer radical polymerization (ATRP) using N-vinylpyrrolidone (VP) as monomer, bromide-terminated poly (D,L-latide) oligomer (Br-PDLLA-Br) as functional macromolecular initiator which was prepared when hydroxy-terminated poly(D,L-latide) oligomer (HO-PDLLA-OH) reacted with 2-bromopropanoyl bromide, CuBr/2,2’-bipyridine complex as the catalyst system. The resulting copolymers were characterized by various analytical techniques. The results showed that the introduction of poly (N-vinylpyrrolidone) (PVP) segments into polylactide enhanced the surface hydrophilicity of the copolymers remarkably and amphiphilic polymer can self-assemble into core-shell structure (polymer micelle) in water by the balance of the hydrophilic and hydrophobic interaction.

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40

Mu, Bin, Ruoping Shen, and Peng Liu. "Facile Preparation of Crosslinked Polymeric Nanocapsules via Combination of Surface-Initiated Atom Transfer Radical Polymerization and Ultraviolet Irradiated Crosslinking Techniques." Nanoscale Research Letters 4, no. 7 (May 6, 2009): 773–77. http://dx.doi.org/10.1007/s11671-009-9311-0.

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41

Hong, Sung Chul, Shijun Jia, Mircea Teodorescu, Tomasz Kowalewski, Krzysztof Matyjaszewski, Amy C. Gottfried, and Maurice Brookhart. "Polyolefin graft copolymers via living polymerization techniques: Preparation of poly(n-butyl acrylate)-graft-polyethylene through the combination of Pd-mediated living olefin polymerization and atom transfer radical polymerization." Journal of Polymer Science Part A: Polymer Chemistry 40, no. 16 (July 9, 2002): 2736–49. http://dx.doi.org/10.1002/pola.10348.

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42

Narayanan, Kannan Badri, Rakesh Bhaskar, and Sung Soo Han. "Recent Advances in the Biomedical Applications of Functionalized Nanogels." Pharmaceutics 14, no. 12 (December 16, 2022): 2832. http://dx.doi.org/10.3390/pharmaceutics14122832.

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Nanomaterials have been extensively used in several applications in the past few decades related to biomedicine and healthcare. Among them, nanogels (NGs) have emerged as an important nanoplatform with the properties of both hydrogels and nanoparticles for the controlled/sustained delivery of chemo drugs, nucleic acids, or other bioactive molecules for therapeutic or diagnostic purposes. In the recent past, significant research efforts have been invested in synthesizing NGs through various synthetic methodologies such as free radical polymerization, reversible addition-fragmentation chain-transfer method (RAFT) and atom transfer radical polymerization (ATRP), as well as emulsion techniques. With further polymeric functionalizations using activated esters, thiol–ene/yne processes, imines/oximes formation, cycloadditions, nucleophilic addition reactions of isocyanates, ring-opening, and multicomponent reactions were used to obtain functionalized NGs for targeted delivery of drug and other compounds. NGs are particularly intriguing for use in the areas of diagnosis, analytics, and biomedicine due to their nanodimensionality, material characteristics, physiological stability, tunable multi-functionality, and biocompatibility. Numerous NGs with a wide range of functionalities and various external/internal stimuli-responsive modalities have been possible with novel synthetic reliable methodologies. Such continuous development of innovative, intelligent materials with novel characteristics is crucial for nanomedicine for next-generation biomedical applications. This paper reviews the synthesis and various functionalization strategies of NGs with a focus on the recent advances in different biomedical applications of these surface modified/functionalized single-/dual-/multi-responsive NGs, with various active targeting moieties, in the fields of cancer theranostics, immunotherapy, antimicrobial/antiviral, antigen presentation for the vaccine, sensing, wound healing, thrombolysis, tissue engineering, and regenerative medicine.

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Pintauer, Tomislav, Wade Braunecker, Edmond Collange, Rinaldo Poli, and Krzysztof Matyjaszewski. "Determination of Rate Constants for the Activation Step in Atom Transfer Radical Polymerization Using the Stopped-Flow Technique." Macromolecules 37, no. 8 (April 2004): 2679–82. http://dx.doi.org/10.1021/ma035634f.

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44

Khezri, Khezrollah, and Yousef Fazli. "Polystyrene/mesoporous diatomite composites by in situ simultaneous reverse and normal initiation technique for atom transfer radical polymerization." Polymer Science, Series B 59, no. 1 (January 2017): 109–16. http://dx.doi.org/10.1134/s1560090417010092.

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45

ZHU, HUI, PENG CHEN, RU XIA, JIASHENG QIAN, JIBIN MIAO, BIN YANG, and LIFEN SU. "EFFECT OF MACROMOLECULAR COUPLING AGENT PMMA-b-PVTES ON STABILIZING NANO-Si3N4." Nano 09, no. 08 (December 2014): 1450095. http://dx.doi.org/10.1142/s1793292014500957.

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Poly(methyl methacrylate)-b-poly(vinyltriethoxysilane) (PMMA-b-PVTES) are synthesized using atom transfer radical polymerization (ATRP) and used as macromolecular coupling agents to modify silicon nitride nanoparticles (nano- Si 3 N 4). The chemical composition of copolymers PMMA-b-PVTES and modified nano- Si 3 N 4 are confirmed by various characterization techniques. The modified nano- Si 3 N 4 shows excellent hydrophobic nature, which make nanoparticles (NPs) stably disperse in organic solvent. Transmission electron microscope (TEM), particle size testing, contact angle measuring and sedimentation experiment are employed to examine the dispersion of modified nano- Si 3 N 4 in chloroform. By comparing the effects of copolymers with varied number-average molecular weight (Mn) and block length ratio on stabilizing nano- Si 3 N 4, we discussed the mechanism of macromolecular coupling agent stabilizing NPs. In our experiments, the copolymer PMMA88-b-PVTES17 is found to be the most effective macromolecular coupling agent for stabilizing nano- Si 3 N 4.

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46

Zhang, Juan, Zhongkai Wang, Xuehui Wang, and Zhigang Wang. "The synthesis of bottlebrush cellulose-graft-diblock copolymer elastomers via atom transfer radical polymerization utilizing a halide exchange technique." Chemical Communications 55, no. 92 (2019): 13904–7. http://dx.doi.org/10.1039/c9cc06982h.

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A novel kind of bottlebrush cellulose-graft-diblock copolymer elastomer (Cell-g-PBA-b-PMMA) was made with cellulose as the backbone chain and poly(n-butyl acrylate)-block-poly(methyl methacrylate) (PBA-b-PMMA) as the diblock copolymer brushes.

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47

Liu, Peng, and Tingmei Wang. "Preparation of Well-Defined Star Polymer from Hyperbranched Macroinitiator Based Attapulgite by Surface-Initiated Atom Transfer Radical Polymerization Technique." Industrial & Engineering Chemistry Research 46, no. 1 (January 2007): 97–102. http://dx.doi.org/10.1021/ie060504r.

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48

Akman, Feride. "Density functional theory (DFT) and Hartree–Fock (HF) calculations of potential p–vinylbenzyl chloride-based macroinitiator for atom transfer radical polymerization." Canadian Journal of Physics 94, no. 3 (March 2016): 290–304. http://dx.doi.org/10.1139/cjp-2015-0665.

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The spectroscopic properties of poly (styrene–co–p–vinylbenzyl chloride) (poly (St-co-VBC)) were investigated by Fourier transform infrared spectroscopy and 1H nuclear magnetic resonance spectroscopic techniques. The molecular geometry and vibrational frequencies of macroinitiator, poly (St-co-VBC), were calculated by using density functional theory (DFT) and Hartree–Fock (HF) methods with 6–31 G+ (d, p) as a basis set. Calculated theoretical values are shown to be in good agreement with that of experimental values. An excellent harmony between the two data sets was verified. Besides, the experimental data of macroinitiator were compared with experimental data of its corresponding monomers such as St and VBC. The dimer and trimer forms of macroinitiator are used as significant contributions for getting an accurate interpretation of the experimental frequencies of poly (St-co-VBC). The results revealed that the change from St and VBC to poly (St-co-VBC) should be characterized by the disappearance of the CH2=CH bonds of the vinyl group and the appearance of the aliphatic C–H and CH2 bonds. The geometrical parameters, Mulliken atomic charges and frontier molecular orbitals energies were also calculated using the same theoretical methods. The chemical shifts were calculated by using the gauge–including atomic orbital method and all the theoretically predicted values were shown to be in good agreement with experimental values. Molecular orbital properties, molecular electrostatic potential, and the potential energy surface for the atom transfer radical polymerization (ATRP) of the macroinitiator were studied with DFT and HF calculations. The potential energy surface of the ATRP initiator is decided by their electronic effect and steric hindrance effect simultaneously.

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Hachimi Alaoui, Chaymaa, Gildas Réthoré, Pierre Weiss, and Ahmed Fatimi. "Sustainable Biomass Lignin-Based Hydrogels: A Review on Properties, Formulation, and Biomedical Applications." International Journal of Molecular Sciences 24, no. 17 (August 30, 2023): 13493. http://dx.doi.org/10.3390/ijms241713493.

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Different techniques have been developed to overcome the recalcitrant nature of lignocellulosic biomass and extract lignin biopolymer. Lignin has gained considerable interest owing to its attractive properties. These properties may be more beneficial when including lignin in the preparation of highly desired value-added products, including hydrogels. Lignin biopolymer, as one of the three major components of lignocellulosic biomaterials, has attracted significant interest in the biomedical field due to its biocompatibility, biodegradability, and antioxidant and antimicrobial activities. Its valorization by developing new hydrogels has increased in recent years. Furthermore, lignin-based hydrogels have shown great potential for various biomedical applications, and their copolymerization with other polymers and biopolymers further expands their possibilities. In this regard, lignin-based hydrogels can be synthesized by a variety of methods, including but not limited to interpenetrating polymer networks and polymerization, crosslinking copolymerization, crosslinking grafted lignin and monomers, atom transfer radical polymerization, and reversible addition–fragmentation transfer polymerization. As an example, the crosslinking mechanism of lignin–chitosan–poly(vinyl alcohol) (PVA) hydrogel involves active groups of lignin such as hydroxyl, carboxyl, and sulfonic groups that can form hydrogen bonds (with groups in the chemical structures of chitosan and/or PVA) and ionic bonds (with groups in the chemical structures of chitosan and/or PVA). The aim of this review paper is to provide a comprehensive overview of lignin-based hydrogels and their applications, focusing on the preparation and properties of lignin-based hydrogels and the biomedical applications of these hydrogels. In addition, we explore their potential in wound healing, drug delivery systems, and 3D bioprinting, showcasing the unique properties of lignin-based hydrogels that enable their successful utilization in these areas. Finally, we discuss future trends in the field and draw conclusions based on the findings presented.

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Sun, Xiaoyi, Hailiang Zhang, Lingjun Zhang, Xiayu Wang, and Qi-Feng Zhou. "Synthesis of Amphiphilic Poly(ethylene oxide)-b-Poly(methyl methacrylate) Diblock Copolymers via Atom Transfer Radical Polymerization Utilizing Halide Exchange Technique." Polymer Journal 37, no. 2 (February 2005): 102–8. http://dx.doi.org/10.1295/polymj.37.102.

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