Topochemical Polymerization of N-Substituted Sorbamides To Provide Thermally Stable and Crystalline Polymers

Matsumoto, Akikazu; Chiba, and Tsuyoshi; Oka, Koichi

doi:10.1021/ma021167a

Cited by 16 publications

(14 citation statements)

References 22 publications

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“…Very recently, we have confirmed that the topochemical polymerization proceeds under UV-and γ-radiation in the crystalline state when naphthylmethyl and higher n-alkyl groups are introduced as the N-substituent of the amide derivatives as expected (7a-7e). 51 The solid-sate polymerization of lithium sorbate (8a) was reported in 1996 by Schlitter and Beck. 52 Most of the topochemical reactions, including our first finding of the topochemical polymerization of 1a have been found accidentally or beyond any expectation.…”

Section: Recent Progress In the Polymerization Of 13-diene Monomers mentioning

confidence: 97%

“…As is briefly described in the previous section, we recently revealed a sheet-type arrangement in the crystals of the sorbamide derivatives (7a-7e) in which linear hydrogen bonds supported the sheet structure and the polymerization occurred between the inter-sheets by the introduction of a naphthylmethyl and long alkyl groups as the N-substituents, resulting in the situation of the diene moieties by the stacking of the sheets in an appropriate sheet-to-sheet distance and phase. 51 …”

Section: Crystal Structure Designmentioning

confidence: 99%

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Polymer Structure Control Based on Crystal Engineering for Materials Design

Matsumoto

2003

Polym J

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111

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ABSTRACT:In this review article, polymer structure control and organic material design based on polymer crystal engineering are described. The structures and properties of crystalline materials are designed using pre-organized molecules through various intermolecular interactions such as hydrogen bonds, π · · · π, CH/π, CH/O, and halogen interactions. Here, we describe the features and mechanisms of the topochemical polymerization of 1,3-diene monomers including some ester, ammonium, and amide derivatives of muconic and sorbic acids, which are 1,3-diene di-and monocarboxylic acid derivatives, respectively. We have proposed the topochemical polymerization principles for diene monomers on the basis of the crystallographic data accumulated for various kinds of diene monomers. The combination of several intermolecular interactions is useful for the construction of molecular packing appropriate for 5 Å stacking in order to facilitate the topochemical polymerization in the crystalline state. We refer to the control of polymer chain structure including tacticity, molecular weight, and ladder structure, and also polymer crystal structures, as well as the organic intercalation system using layered polymer crystals obtained by the topochemical polymerization. A totally solvent-free system for the synthesis of layered polymer crystals is also described.KEY WORDS Topochemical Polymerization / Solid-State Reaction / Crystal Engineering / Supramolecular Synthon / Stereoregular Polymer / Controlled Radical Polymerization / X-Ray Single Crystal Structure Analysis / Intercalation / Controlled polymer synthesis, including the control of polymer chain structures such as molecular weight, molecular weight distribution, chain-end structure, branching, regioselectivity, and stereoselectivity, has great potential for the design of macromolecular architecture leading to advanced nano-materials and devices. [1][2][3][4][5][6][7][8][9][10][11] All the features and functions of polymers importantly depend on primary chain structures and the manner of polymer chain assembly in crystalline and non-crystalline solids, or in a condensed state. Therefore, the control of polymer chain structures in polymer synthesis can hardly be overestimated for the architecture of advanced polymeric materials.Especially, the stereochemistry of polymers has received significant attention in both fundamental and applied fields ever since the first discoveries of stereoregular polymers in the 1950s. 12-14 Highly controlled stereospecific polymerization has been well established by coordination polymerization of olefins and diene monomers and by anionic polymerization of certain types of polar monomers. Radical polymerization is the most important and convenient process for the production of various kinds of vinyl and diene polymers due to recent achievements in well-controlled polymerizations in addition to the classical advantages of the radical process. [15][16][17][18][19][20][21][22] There are two fundamentally different ways to control of the chain structu...

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Section: Recent Progress In the Polymerization Of 13-diene Monomers mentioning

confidence: 97%

Section: Crystal Structure Designmentioning

confidence: 99%

Polymer Structure Control Based on Crystal Engineering for Materials Design

Matsumoto

2003

Polym J

Self Cite

111

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“…Therefore, a mixed microstructure, resulting from polymerization switching between zig‐zag and helical propagation is in line with both NMR and CD spectral evidence. In the presence of 2 a or 2 b there is no change in tacticity of the polymerization;33, 34 rather it introduces a bias of the absolute stereochemistry with which the helical propagation proceeds. Therefore it resembles in many aspects the “majority rules” principle pioneered by Green 13…”

Section: Methodsmentioning

confidence: 99%

Chiral Amplification in the Transcription of Supramolecular Helicity into a Polymer Backbone

et al. 2005

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“…In contrast to the results of the successful polymerization of the ammonium and ester derivatives during the last decade, no polymerization has been reported for the amide derivatives of the 1,3-diene carboxylic acids, except for the case of N-octadecylsorbamide [25]. Recently, Matsumoto et al confirmed that the topochemical polymerization proceeds under UV and g-ray irradiation in the crystalline state when naphthylmethyl and higher n-alkyl groups are introduced as the N-substituent of the amide derivatives as expected [85]. During polymerization of the sorbamides, polymerization proceeded in a direction different from that of the 1D hydrogen bond chain despite the appropriate stacking distance.…”

Section: Hydrogen Bond Networkmentioning

confidence: 97%