Topochemical Polymerization of 1-Naphthylmethylammonium Sorbate and Characterization of the Resulting Stereoregular Polymer

Matsumoto, Akikazu; Odani, Toru

doi:10.1295/polymj.31.717

Cited by 12 publications

(7 citation statements)

References 13 publications

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“…In our earlier work (ref ), we reported no polymerization of 2a under UV-irradiation at room temperature for 8 h, contrary to the results in this study. It is due to the polymorphs.…”

Section: Referencescontrasting

confidence: 99%

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

2003

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“…In our earlier work (ref ), we reported no polymerization of 2a under UV-irradiation at room temperature for 8 h, contrary to the results in this study. It is due to the polymorphs.…”

Section: Referencescontrasting

confidence: 99%

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

2003

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“…47,48 The polymerization of the ammonium derivatives of sorbic acid has also been revealed (5a-5c and 6a). 48,49 A naphthylmethylammonium group is very useful for the design of various polymerizable 1,3-diene monomers other than muconic and sorbic acids but also for other types of 1,3-diene carboxylic acids (9a-9e). 50 In contrast to the results of the successful polymerization of the ammonium and ester derivatives during the recent decade, no polymerization has been reported for the amide derivatives of the 1,3-diene carboxylic acids except for only the case of N-octadecylsorbamide (7d).…”

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

confidence: 99%

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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“…9−12 They discovered that crystalline-state polymerization of the bulky 1-naphthylmethylammonium salt of sorbic acid occurred stereospecifically to give the 1,4-trans-erythrodiisotactic polymer. 10 However, the polymerizations of alkyl sorbates in both the crystal state or solution were difficult to be stereospecifically controlled to such a high degree.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The recent advances in controlled/living radical polymerization improve these problems to some extent by greatly reducing the radical concentration. − Several other effective polymerization approaches have so far been reported to study the polymerization feature of the polar conjugated dienes and the stereochemical control of the formed polymer products. For instance, Matsumoto et al first realized the crystalline-state (topochemical) 1,4-polymerization of diethyl cis , cis -muconate to yield a regulated stereochemical chain structure and ultrahigh molecular weight by photoirradiation of the monomer crystals and then designed and synthesized lots of crystallizable sorbates, sorbamides, and muconates for further study. − They discovered that crystalline-state polymerization of the bulky 1-naphthylmethylammonium salt of sorbic acid occurred stereospecifically to give the 1,4- trans - erythro -diisotactic polymer . However, the polymerizations of alkyl sorbates in both the crystal state or solution were difficult to be stereospecifically controlled to such a high degree.…”

Section: Introductionmentioning

confidence: 99%

Organocatalyzed Group Transfer Polymerization of Alkyl Sorbate: Polymer Synthesis, Postpolymerization Modification, and Thermal Properties

Liu

Chen

2021

Macromolecules

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The current work presents the organocatalyzed group transfer polymerization (GTP) of alkyl sorbate, the postpolymerization modification at the double bond of the poly(alkyl sorbate) (PAS) backbone, and its thermal properties. The selected alkyl sorbate includes ethyl, n-hexyl, and n-octadecyl sorbate with the carbon number of the n-alkyl side chain being three times between every two neighboring monomers. The polymerization kinetics and mechanisms are briefly discussed for both the t-Bu-P4- and Me3SiNTf2-catalyzed GTPs of ethyl sorbate. Both of the two GTPs only undergo 1,4-addition to produce trans-rich PASs in which the former affords 81.9–85.4% trans content and the latter a much higher value as trans > 96%. The hydrogenation and epoxidation of the internal double bond turn out to be quantitative to provide the hydrogenated and epoxidized polymers, PAS-H2 and PAS-epoxy. The hydrogenation process makes the diastereochemistry and stereoregular structures of the two chiral carbons in the monomeric unit distinguishable by 13C NMR spectra, from which we know that the t-Bu-P4-catalyzed GTP produces erythro-rich PASs (erythro content = ca. 64%), while the Me3SiNTf2-catalyzed GTP gives relatively threo-rich PASs (threo content = 56–58%). However, the diisotactic/disyndiotactic ratios determined by 13C NMR spectra do not show an obvious difference between each other. Thermogravimetric analyses suggest that PAS-H2 shows the highest thermal stability and PAS-epoxy the lowest, due to the different polarity of the newly formed C–C bond in the main chain before and after the chemical modification of the internal double bond. For the amorphous poly(ethyl sorbate) (PES) and poly(n-hexyl sorbate) (PHS), change of the ethyl side group to n-hexyl greatly decreases the glass transition temperature (T g). As for the same PES/PHS series polymers, either the hydrogenation or the epoxidation of the internal double bond drastically changes the T g value of the final polymer product. In addition, the ca. 10% difference in the trans-cis composition for unmodified PES or PHS almost has no effect on T g values, while the erythro/threo content shows a prominent influence for the chemically modified polymers as the T g value can be changed from several to tens of Celsius degree when the same polymer changes from erythro-rich to threo-rich. On the contrary, crystallizable poly(n-octadecyl sorbate) (PODS) and its modified polymers possess melting points (T m) in a pretty narrow temperature range of 34.7–41.4 °C, which is almost the same as the T m of n-octadecyl sorbate. It is likely that the T m values of PODS and its derivative polymers are only determined by the crystallization of the long n-octadecyl side chain, almost irrespective of the chain length, the trans-cis isomerization, the diastereochemistry, and the stereochemistry of the main chain.

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Topochemical Polymerization of 1-Naphthylmethylammonium Sorbate and Characterization of the Resulting Stereoregular Polymer

Cited by 12 publications

References 13 publications

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

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

Polymer Structure Control Based on Crystal Engineering for Materials Design

Organocatalyzed Group Transfer Polymerization of Alkyl Sorbate: Polymer Synthesis, Postpolymerization Modification, and Thermal Properties

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