Topochemical Polymerization of 1,3-Diene Monomers and Features of Polymer Crystals as Organic Intercalation Materials

Matsumoto, Akikazu; Odani, Toru

doi:10.1002/1521-3927(20011001)22:15<1195::aid-marc1195>3.0.co;2-k

Cited by 79 publications

(55 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…During the recent decade, we have revealed the features and mechanisms of the polymerization of various 1,3-diene monomers, 37,38 including the esters, the amides, and the alkylammonium salts of (Z, Z)-or (E, E)-muconic and sorbic acids, via a topochemical reaction mechanism in the crystalline state, and the characterization of the obtained polymer crystals as a new category of organic solids ( Figure 1). …”

mentioning

confidence: 79%

“…52 Most of the topochemical reactions, including our first finding of the topochemical polymerization of 1a have been found accidentally or beyond any expectation. 38,39 During subsequent and extensive investigation, numerous studies have been carried out by trialand-error approaches to establish any empirical rule accounting for a correlation between the geometry of functional moieties and reactions in the solid state. The sophisticated control of molecular stacking for any function or reaction is required, but still lacking at present.…”

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

confidence: 99%

See 1 more Smart Citation

Polymer Structure Control Based on Crystal Engineering for Materials Design

Matsumoto

2003

Polym J

Self Cite

111

View full text Add to dashboard Cite

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...

show abstract

mentioning

confidence: 79%

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

Self Cite

111

View full text Add to dashboard Cite

show abstract

“…Several diyne and diene monomers undergo solidstate polymerization, leading to polymers with controlled chemical and stereostructures. [41][42][43][44][45][46][47] However, there has been no clear examples of solid-state polymerization of vinyl monomers, except for the reactions using solid matrices (inclusion polymerization) [48][49][50][51][52] and the DBF polymerization described here. 17 Although the details are still under investigation, cationic initiators can also effectively polymerize DBF.…”

Section: Dpe Dbf Styrenementioning

confidence: 99%

Synthesis, structure and function of π-stacked polymers

Nakano

2010

Polym J

128

101

View full text Add to dashboard Cite

Macromolecular conformation often has a significant effect on the properties of polymeric materials, and hence, conformational control in synthesizing a polymer is an important goal in polymer science. As a new conformational motif of vinyl polymers having side-chain p-electronic groups, we have introduced a 'p-stacked structure' in which side-chain chromophores are regularly stacked on top of each other and main-chain C-C bonds have a nearly all-trans, zigzag conformation. p-Stacked polymers can be prepared by vinyl polymerization of dibenzofulvene (DBF) and its derivatives. On the basis of the controlled structure, poly(DBF) and its derivatives exhibit unique photophysical and electronic properties as vinyl polymers. In addition, introduction of chirality to p-stacked polymers was also achieved. In this review, the synthesis of poly(DBF) and its derivatives and their structural analyses and properties are described. Polymer Journal (2010) 42, 103-123; doi:10.1038/pj.2009 Keywords: charge transport; chirality; dibenzofulvene; helix; photophysical properties; p-stacked structureIn designing functional organic materials with desired properties, spatial arrangement control of constituent molecules is an important factor because molecules in a regulated assembly often indicate properties different from those in solution or in gas phase because of specific intermolecular interactions. Effective molecular assembly control can be achieved by arrangement of functional molecules as a part of a polymer chain with a regulated conformation and configuration in which the polymer backbone functions as a structural template or scaffold. This is possible either by polymerizing functional molecules as monomers or by attaching functional molecules through a chemical reaction to a polymer chain. In the former case, the functional molecules to be aligned need to have a polymerizable moiety such as a vinyl group; they are a part of monomers and become constituents of a polymer chain as a part of monomeric units, typically as side-chain groups. The monomer structure itself may significantly contribute to the formation of a regulated polymer chain structure through intermolecular repulsion or attraction. An advantage of these polymer-based methods over other methodologies developed mainly for low-molecular-weight compounds based on the accumulation of relatively weak forces is that molecular orders formed along a polymer chain are generally stable due to covalent bonds. Moreover, using a polymer chain, a very tight or close packing of molecules (monomeric units), which is not plausible for the method based on weak intermolecular attractions, is possible when the enthalpy gain in covalent bond formation by polymerization or by polymer reaction outweighs the loss in free energy in packing molecules tightly into a small space around the polymer chain.Although these polymer-based methods generally require more synthetic efforts than intermolecular-force-based methods, a wider variety of molecular orders may be possible on the basis of re...

show abstract

“…In the late 1960s, two typical examples of topochemical polymerization were discovered: stepwise [2+2] photopolymerization of 2,5-styrylpyradine and its analogous diolefins [11] and thermal or radiation polymerization of diacetylenic derivatives [12]. Thirty years later, Matsumoto et al discovered the topochemical polymerization of various kinds of conjugated 1,3-diene monomers giving a highly stereoregular polymer in the form of polymer crystals [13,14]. When a (Z,Z)-muconic ester was photoirradiated in the crystalline state, a mesodiisotactic 2,5-trans (tritactic) polymer was produced, in contrast to the formation of an atactic polymer by conventional radical polymerization in an isotropic state.…”

Section: Introductionmentioning

confidence: 99%