[신간의 별자리x] 우리/미술, 그리고 ‘슬픔의 박물관’

Atom transfer radical polymerization.

New polymer synthesis by nitroxide mediated living radical polymerizations.

Following Sharpless' visionary characterization of several idealized reactions as click reactions, the materials science and synthetic chemistry communities have pursued numerous routes toward the identification and implementation of these click reactions. Herein, we review the radical-mediated thiol-ene reaction as one such click reaction. This reaction has all the desirable features of a click reaction, being highly efficient, simple to execute with no side products and proceeding rapidly to high yield. Further, the thiol-ene reaction is most frequently photoinitiated, particularly for photopolymerizations resulting in highly uniform polymer networks, promoting unique capabilities related to spatial and temporal control of the click reaction. The reaction mechanism and its implementation in various synthetic methodologies, biofunctionalization, surface and polymer modification, and polymerization are all reviewed.

Thiol–Ene Click Chemistry

비만아 부모의 돌봄 경험: q 방법론

After an introduction reporting the properties and the applications of fluoropolymers, a first part deals with i) the main routes to produce vinylidene fluoride (VDF) monomer, ii) its homopolymerization, and iii) the advantages and uses of polyvinylidene fluoride (PVDF). In a second section, this review, illustrated by numerous examples, extensively reports the synthesis, properties and applications of the copolymers based on VDF with non-halogenated, fluorinated, commercially available or synthesized comonomers. These comonomers exhibit XYC=CZ-Sp-R structures where X, Y, and Z represent H, F, and CF3 groups, Sp a spacer and R a function such as OH, OAc, SAc, CO2R' (R' being a H atom or an alkyl group), CN, P(O)(OR')2 and SO3H. According to the nature and to the amount of the comonomer, the copolymers can be thermoplastic, elastomeric or thermoplastic elastomers. Introducing reactive R side groups brings complementary properties such as hydrophily, ionic exchange or surface properties, or further crosslinking of the resulting copolymers. Then, the kinetics of radical copolymerization of VDF with M comonomers led to the assessment of the reactivity ratios which are compared. Hence, a reactivity series of these M comonomers with respect to a macroradical terminated by VDF is proposed. Usually, these copolymers exhibit random structures but only three comonomers produced alternating copolymers with VDF: hexafluoroisobutylene, F2C=CFCO2CH3, and H2C=C(CF3)CO2R. The controlled radical copolymerizations of VDF with other comonomers (such as chlorotrifluoroethylene, 3,3,3-trifluoropropene, hexafluoropropylene, perfluoromethyl vinyl ether or-trifluoromethacrylic acid) either in the presence of xanthates, borinates or iodo-compounds are also reported. In addition, new VDF-containing copolymers exhibit well-defined architectures, such as block and graft copolymers. They can be synthesized either by conventional techniques or by controlled radical copolymerization. Chemical modifications of PVDF and poly(VDF-co-monomer) copolymers are also presented. Several properties and applications (such as surfactants, dielectrical polymers, thermoplastic elastomers, fuel cell and ultrafiltration membranes, or polycondensates, the fluorinated segments of which bringing softness and thermal stability) of these VDF-containing copolymers will illustrate this review.

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From vinylidene fluoride (VDF) to the applications of VDF-containing polymers and copolymers: recent developments and future trends.

Polymeric materials as anion-exchange membranes for alkaline fuel cells

Iodocompounds are highly attractive as potential intermediates for the synthesis of various organic and macromolecular molecules because of the ability of the iodine atom to be a good leaving atom. In addition, they are efficient transfer agents in radical polymerization. In fact, the ability of the iodine atom to transfer onto growing macromolecular chains allowed the development of such compounds. An important class of iodocompounds employed as chain transfer agents (CTAs) are the fluorinated iodocompounds, R FI. These compounds could be obtained in good yield by simple addition of either HI or ICl onto fluorovinylic monomers. These fluorinated CTAs enabled both initiation of the polymerization under UV, thermally or in the presence of redox catalysis, and transfer of the iodine atom onto the growing chains. Oligomers of low molar masses could then be obtained. Then, in the late 1970s, Tatemoto 1 pened the route to the iodine transfer polymerization (ITP). Hence, by using an initiating radical, iodofluorocompounds could enter in a controlled process, based on a degenerative transfer (DT). This real breakthrough was first realized with fluoroolefin monomers but was rapidly extended to other common nonhalogenated vinyl monomers. For specific applications, nonfluorinated CTAs were preferred. Some iodoalkanes, such as iodoform, were then investigated in the ITP process. Recently, reverse iodine transfer polymerization (RITP), another DT process, was discovered by us and is based on the use of molecular iodine. It was thus of interest to deeper summarize the synthesis and the use of iodinated derivatives involved in telomerization, ITP, and RITP, and these are the objectives of this review, divided in four main parts. The first part reports the syntheses of such iodocompounds, fluorinated and nonfluorinated ones. The structural requirements are also investigated for further efficient transfer reactions. The following parts describe their uses in several radical processes, i.e., telomerization, ITP, and RITP. A wide range of vinyl monomers (halogenated and nonhalogenated) have been involved in these radical techniques. Then, syntheses of well-architectured copolymers (especially block * To whom correspondence should be addressed. Tel: (0033)4 67 14 43 01. Fax: (0033)4 67 14 72 20. E-mail: bernard.boutevin@enscm.fr. 3936 Chem. Rev. 2006, 106, 3936−3962

Use of iodocompounds in radical polymerization.

Chemical reactions of polymer crosslinking and post-crosslinking at room and medium temperature

https://hal.archives-ouvertes.fr/hal-00382623/document

Bruno Ameduri

Papers

From vinylidene fluoride (VDF) to the applications of VDF-containing polymers and copolymers: recent developments and future trends.

Polymeric materials as anion-exchange membranes for alkaline fuel cells

Use of iodocompounds in radical polymerization.

Chemical reactions of polymer crosslinking and post-crosslinking at room and medium temperature

Functional fluoropolymers for fuel cell membranes