Living-Free-Radical Emulsion Photopolymerization of Methyl Methacrylate by a Surface Active Iniferter (Suriniferter)
A novel surface-active RAFT agent as a suriniferter, composed of the dithiobenzoyl main structure and a benzoic hydrophobic carboxylate hydrophilic moiety, was synthesized and applied to the living-radical emulsion polymerization of methyl methacrylate (MMA) initiated by UV irradiation in the absenc...
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Published in | Macromolecules Vol. 36; no. 21; pp. 7994 - 8000 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
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American Chemical Society
21.10.2003
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Abstract | A novel surface-active RAFT agent as a suriniferter, composed of the dithiobenzoyl main structure and a benzoic hydrophobic carboxylate hydrophilic moiety, was synthesized and applied to the living-radical emulsion polymerization of methyl methacrylate (MMA) initiated by UV irradiation in the absence of added surfactant and additional initiator at various temperatures. A stable spherical bead of PMMA was successfully obtained using the suriniferter, maintaining the living-radical polymerization characteristics. Monomer conversion, molecular weight evolution and distribution, and final particle sizes were characterized. The higher the iniferter concentration, the higher the conversion and the lower the molecular weight, final particle size, and molecular weight distribution (PDI) obtained. A linear increase in molecular weight with respect to conversion is observed, implying that this technique using the suriniferter follows living-radical polymerization. The PDI varies from 1.21 to 1.43, and the final particle sizes vary from 407 to 304 nm with an increase in the polymerization temperature from 60 to 80 °C. The ratios of the triad tacticity for syndiotactic, atactic, and isotactic configurations of the synthesized PMMA are 54.3, 38.6, and 7.1, respectively, and the glass-transition temperature (T g) is 126.6 °C, which is much higher than that of commercial PMMA (T g = 105 °C). Thus, it is believed that the suriniferter used in living-free-radical emulsion polymerization modifies the stereoregularity of the PMMA. |
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AbstractList | A novel surface-active RAFT agent as a suriniferter, composed of the dithiobenzoyl main structure and a benzoic hydrophobic carboxylate hydrophilic moiety, was synthesized and applied to the living-radical emulsion polymerization of methyl methacrylate (MMA) initiated by UV irradiation in the absence of added surfactant and additional initiator at various temperatures. A stable spherical bead of PMMA was successfully obtained using the suriniferter, maintaining the living-radical polymerization characteristics. Monomer conversion, molecular weight evolution and distribution, and final particle sizes were characterized. The higher the iniferter concentration, the higher the conversion and the lower the molecular weight, final particle size, and molecular weight distribution (PDI) obtained. A linear increase in molecular weight with respect to conversion is observed, implying that this technique using the suriniferter follows living-radical polymerization. The PDI varies from 1.21 to 1.43, and the final particle sizes vary from 407 to 304 nm with an increase in the polymerization temperature from 60 to 80 °C. The ratios of the triad tacticity for syndiotactic, atactic, and isotactic configurations of the synthesized PMMA are 54.3, 38.6, and 7.1, respectively, and the glass-transition temperature (T g) is 126.6 °C, which is much higher than that of commercial PMMA (T g = 105 °C). Thus, it is believed that the suriniferter used in living-free-radical emulsion polymerization modifies the stereoregularity of the PMMA. |
Author | Jung, Hyejun Shim, Sang Eun Lee, Kangseok Choe, Soonja Shin, Yoda Jun, Jong Won |
Author_xml | – sequence: 1 givenname: Sang Eun surname: Shim fullname: Shim, Sang Eun – sequence: 2 givenname: Yoda surname: Shin fullname: Shin, Yoda – sequence: 3 givenname: Jong Won surname: Jun fullname: Jun, Jong Won – sequence: 4 givenname: Kangseok surname: Lee fullname: Lee, Kangseok – sequence: 5 givenname: Hyejun surname: Jung fullname: Jung, Hyejun – sequence: 6 givenname: Soonja surname: Choe fullname: Choe, Soonja |
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Cites_doi | 10.1021/ma9804951 10.1002/marc.1982.030030208 10.1021/ma011840g 10.1021/ma001205v 10.1002/1097-0126(200009)49:9<993::AID-PI506>3.0.CO;2-6 10.1002/macp.1983.021840409 10.1016/S0079-6700(02)00008-4 10.1021/ma0204296 10.1007/978-1-4899-3176-4 10.1006/jcis.2001.7430 10.1016/0014-3057(94)00122-7 10.1002/macp.1958.020270112 10.1002/pol.1977.170150912 10.1021/ie0009482 10.1021/ma00063a054 10.1021/ma00109a056 10.1007/BF00955715 10.1021/bk-1998-0685 10.1021/ma0013298 10.1021/ma00128a012 10.1021/ma00127a042 10.1007/BF00254997 10.1021/ma012214m 10.1016/0032-3861(93)90636-O 10.1016/S0079-6700(01)00033-8 |
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Keywords | Tacticity Particle size Priming activity Living polymer Methyl methacrylate polymer Dithioester Experimental study Property processing relationship Latex Photoinitiator Anionic surfactant Chain transfer Emulsion polymerization Photopolymerization Carboxylate Chemical synthesis |
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SubjectTerms | Applied sciences Exact sciences and technology Physicochemistry of polymers Polymerization Polymers and radiations |
Title | Living-Free-Radical Emulsion Photopolymerization of Methyl Methacrylate by a Surface Active Iniferter (Suriniferter) |
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