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Microenvironment and functional group mobility of macroporous network polymers
224 The unique property of gelatin on the photosensitized charge separation in gelatin hydrogel/Co(III)-Schiff base complex/Ru(bpy)~ + [1] and the present systems have been discussed in the light of the results obtained. 1 Y. Kurimura, K. Hiramatsu, T. Harakawa, M. Yamashita, Y. Osada, K. Shigehara and A. Yamada, J. Chem. Soc.,
Faraday Trans., (1990) 609.
Synthesis and Reactions of Uniform Size Telechelic Polysiloxanes Y. Tezuka, H. Kazama and K. Imai, Department of Material Science and Technology, Nagaoka
University of Technology, Kamitomioka, Nagaoka, Niigata 940-21, Japan Uniformly sized prepolymers possessing suitably reactive end groups are considered to be important as macromolecular building blocks for the synthesis of block and graft copolymers with a precise macromolecular architecture. In the present paper, we will report on the syntheses and reactions of uniform size poly(dimethylsiloxane)s, poly(DMS)s, ha~ng various reactive end groups. The monofunctional and, in particular, the bifunctional living poly(DMS) were produced by the appropriate choice of initiators in the anionic ring-opening polymerization of hexamethylcyclotrisiloxane (D3). The subsequent termination reaction with dimethylchlorosilane provided the monoand bi-functional uniform size poly(DMS) with a silane end group. The hydrosilation reaction of a silane function with various allylic compounds, such as allyl alcohol, N, N-dimethyl allylamine and allylic diol, introduced various functional groups at the single and both ends of the poly(DMS) chain. The hydroxyl end group was then subjected to a further modification reaction to covert it to an electrophilic group like a tosylate and a pyrrolidinium salt group for reaction with nucleophiles. Termination with newly synthesized chlorosilane derivatives having a protected carboxylic acid group allowed the production of telechelic poly(DMS)s with carboxylic acid groups. A variety of uniform size telechelic poly(DMS) s thus produced were employed for polymer reactions to produce block, graft and network copolymers of well defined poly(DMS) segment. Published in Polym. Bull., 21 (1989) 31; Polym. J., 19 (1987) 1091; Makromol. Chem., 189 (1988) 895; Polymer, 30 (1989) 553; Polym. Plast. Technol. Eng., 28 (1989) 109; Macromolecules, 24 (1991) 122.
Microenvironment and Functional Group Mobility of Macroporous Network Polymers K.J. Shea, University of California, Irvine, Irvine, CA 92717, USA Macroporous network polymers are structurally complex, inhomogeneous materials that are of considerable value as supports for catalysts. We will discuss applications of fluorescence spectroscopy, FT-IR, and C P / M A S - N M R spectroscopy for the analysis of these materials. Comparisons will be drawn between synthetic polymeric catalysts and those that occur in nature (enzymes). To be published in Macromolecules, 24 (1991) and in J. Am. Chem. Soc., 113 (1991).
Recent Work on Polymer-Supported Asymmetric Synthesis P. Hodge, Chemistry Department, University of Manchester, UK Asymmetric organic synthesis using polymer-supported (PS) chiral catalysts is one of the most useful types of PS organic reaction. However, such systems are also potentially a sensitive means of probing PS reaction systems because the ee's obtained in asymmetric syntheses are generally very sensitive to the various reaction parameters. Reaction 1 catalysed by B-aminoalcohols, which has been studied by other research groups [1,2], appeared to be a particularly attractive reaction to probe polymer effects because the reaction taken place slowly even in the absence of added catalysts, i.e., a competitive situation exists. This prompted us to study the ee's obtained in reaction 1 using PS
Faraday Trans., (1990) 609.
Synthesis and Reactions of Uniform Size Telechelic Polysiloxanes Y. Tezuka, H. Kazama and K. Imai, Department of Material Science and Technology, Nagaoka
University of Technology, Kamitomioka, Nagaoka, Niigata 940-21, Japan Uniformly sized prepolymers possessing suitably reactive end groups are considered to be important as macromolecular building blocks for the synthesis of block and graft copolymers with a precise macromolecular architecture. In the present paper, we will report on the syntheses and reactions of uniform size poly(dimethylsiloxane)s, poly(DMS)s, ha~ng various reactive end groups. The monofunctional and, in particular, the bifunctional living poly(DMS) were produced by the appropriate choice of initiators in the anionic ring-opening polymerization of hexamethylcyclotrisiloxane (D3). The subsequent termination reaction with dimethylchlorosilane provided the monoand bi-functional uniform size poly(DMS) with a silane end group. The hydrosilation reaction of a silane function with various allylic compounds, such as allyl alcohol, N, N-dimethyl allylamine and allylic diol, introduced various functional groups at the single and both ends of the poly(DMS) chain. The hydroxyl end group was then subjected to a further modification reaction to covert it to an electrophilic group like a tosylate and a pyrrolidinium salt group for reaction with nucleophiles. Termination with newly synthesized chlorosilane derivatives having a protected carboxylic acid group allowed the production of telechelic poly(DMS)s with carboxylic acid groups. A variety of uniform size telechelic poly(DMS) s thus produced were employed for polymer reactions to produce block, graft and network copolymers of well defined poly(DMS) segment. Published in Polym. Bull., 21 (1989) 31; Polym. J., 19 (1987) 1091; Makromol. Chem., 189 (1988) 895; Polymer, 30 (1989) 553; Polym. Plast. Technol. Eng., 28 (1989) 109; Macromolecules, 24 (1991) 122.
Microenvironment and Functional Group Mobility of Macroporous Network Polymers K.J. Shea, University of California, Irvine, Irvine, CA 92717, USA Macroporous network polymers are structurally complex, inhomogeneous materials that are of considerable value as supports for catalysts. We will discuss applications of fluorescence spectroscopy, FT-IR, and C P / M A S - N M R spectroscopy for the analysis of these materials. Comparisons will be drawn between synthetic polymeric catalysts and those that occur in nature (enzymes). To be published in Macromolecules, 24 (1991) and in J. Am. Chem. Soc., 113 (1991).
Recent Work on Polymer-Supported Asymmetric Synthesis P. Hodge, Chemistry Department, University of Manchester, UK Asymmetric organic synthesis using polymer-supported (PS) chiral catalysts is one of the most useful types of PS organic reaction. However, such systems are also potentially a sensitive means of probing PS reaction systems because the ee's obtained in asymmetric syntheses are generally very sensitive to the various reaction parameters. Reaction 1 catalysed by B-aminoalcohols, which has been studied by other research groups [1,2], appeared to be a particularly attractive reaction to probe polymer effects because the reaction taken place slowly even in the absence of added catalysts, i.e., a competitive situation exists. This prompted us to study the ee's obtained in reaction 1 using PS