This Perspective presents the development in living anionic polymerization since 1990. The main subjects involve following concerns of polymerization: functional styrene derivatives, new monomers and promising additives, regio- stereoselective polymerization, special polymers having rigid-rod-like or helical conformations, synthesis complex branched composed comblike segments via poly(macromonomer)s, precise macromolecular architectures including multiblock polymers, exact graft...

Two kinds of polyhedral oligomeric silsesquioxane (POSS)-containing block copolymers (BCPs), namely PS-b-PMAPOSS and PMMA-b-PMAPOSS, were synthesized by living anionic polymerization. A wide range molecular weights obtained with a very narrow polydispersity index less than 1.09. The bulk samples prepared slow evaporation from polymer solution in chloroform exhibit well-defined microphase-separated structures long-range order. Thermal annealing induced hierarchical consisting smaller length...

This communication reports on the design and synthesis of mechanochromophores with a dynamic covalent system composed tetraarylsuccinonitrile skeleton that generate metastable organic luminescent carbon radical.

Mechanoresponsive polymers can have attractive functions; however, the relationship between polymer architecture and mechanoresponsiveness in bulk state is still poorly understood. Here, we designed well-defined linear star with a mechanophore at center of each architecture, investigated effect molecular weight branched structures on solid state. Diarylbibenzofuranone, which undergo homolytic cleavage central C-C bond by mechanical force to form blue-colored radicals, was used as because...

Abstract Intrinsically exchangeable dynamic covalent bonds that can be triggered by readily usable stimuli offer easy incorporation of their properties in various molecular systems, but the library such is still being developed. Herein, we report chemistry 2,2,6,6‐tetramethylpiperidine‐1‐sulfanyl (TEMPS) dimers derived from thermally reversible homolytic dissociation disulfide linkages. High air stability TEMPS was observed even at 100 °C, affording facile employment thermal...

A facile approach to polymethacrylate networks that contain thermally exchangeable bis(2,2,6,6-tetramethylpiperidin-1-yl)disulfide (BiTEMPS) cross-linkers is reported, and the easily inducible healability reprocessability of obtained are discussed. The free radical polymerization BiTEMPS hexyl methacrylate (HMA) monomers afforded insoluble colorless poly(hexyl methacrylate) (PHMA) films, whose structures were characterized after de-cross-linking via thermal exchange reactions with added...

Polymer–inorganic composites with diarylbibenzofuranone (DABBF) moieties, dynamic covalent mechanochromophores, were prepared, and their mechanochromic behavior was systematically investigated. The central C–C bonds in DABBF moieties can be cleaved by mechanical force to form the corresponding stable blue radicals, which quantitatively evaluated electron paramagnetic resonance (EPR) spectroscopy. One controversial issue but attractive property system is equilibrium between activated...

Mechanochromic polymers, which react to mechanical force by changing color, are expected find applications in smart materials such as damage sensors. Although numerous types of mechanochromic polymers have been reported so far, developing that can recognize different stimuli remains a formidable challenge. Materials not only change their color response stimulus but also detect its nature should be great importance for practical applications. In this paper, we report our preliminary findings...

Mechanochromic polymers, that is, polymers sensitive to mechanical impact, promise great potential for applications in damage sensors. In particular, radical-type mechanochromic which produce colored radical species response stress, may enable not only the visualization of but also its quantitative evaluation by electron paramagnetic resonance analysis. Herein, a polymer exhibits color change from white green upon dissociation diarylbibenzothiophenonyl moiety at mid-point polystyrene chain...

Abstract The growth of lamellar crystals has been studied in particular for spherulites polymeric materials. Even though such spherulitic structures and their are crucial importance the mechanical optical properties resulting materials, several issues regarding residual stress remain unresolved wider context crystal growth. To gain further insight into micro-mechanical forces during crystallization process herein, we introduce tetraarylsuccinonitrile (TASN), which generates relatively stable...

Surface mechanochemistry of nanocelluloses modified with a dynamic covalent mechanophore is investigated, and self-healing composites the celluloses are developed.

Abstract Control over mechanochemical polymer scission by another external stimulus may offer an avenue to further advance the fields of chemistry, mechanochemistry, and materials science. Herein, we demonstrate that light can regulate behavior a diarylethene-conjugated Diels–Alder adduct (DAE/DA) reversibly isomerizes from weaker open form stronger closed under photoirradiation. Pulsed ultrasonication experiments, spectroscopic analyses, density functional theory calculations support...

Mechanochromism, a color change induced by mechanical force, has attracted much attention in materials science, as it can be used to create stress- and damage-detecting sensors. In particular, radical-type mechanochromic molecules (mechanochromophores), which produce colored radicals upon exposure enable the qualitative visualization of stress quantitative evaluation generated radical species electron paramagnetic resonance spectroscopy. However, sensitivity mechanochromophores thermal...

Mechanochromism can be triggered by different mechanical stimuli, such as tension, compression, shearing, and sonication. Freezing a polymer gel also induces stress on the network. Herein, freezing-induced mechanoluminescence is demonstrated for first time introduction of tetraarylsuccinonitrile moiety light-emitting mechanochromophore at cross-linking points network, in which not only color change but light emission. The detailed mechanism characteristics this were quantitatively evaluated...

This article reviews the synthesis of well-controlled graft polymers by living anionic polymerization towards exact polymers. The structure a polymer is defined following three parameters: (1) molecular weight main chain, (2) and (3) placement chain. Based on these parameters, extent structural control synthesized so far described. Finally, recently (co)polymers stepwise iterative methodologies are introduced. In their structures, parameters perfectly controlled.

We report the synthesis of poly(5-hexyl-2-vinylthiophene) (PVT) and poly(5-hexyl-5′′-vinyl-2,2′:5,2′′-terthiophene) (PVTT) as charge storage electrets for nonvolatile organic field effect transistor (OFET) memory devices n-type semiconducting N,N′-bis(2-phenylethyl)perylene-3,4,9,10-bis(dicarboximide) (BPE-PTCDI). The effects conjugated thiophene chain length on morphology, OFET mobility characteristics are explored compared to those styrene or fluorene side chain. device using PVTT an...

A repeating 1:1 addition reaction using 1,1-diphenylethylene (DPE) derivatives, known as "living anionic (LAAR)," was performed to construct defect-free DPE sequences composed of nonhomopolymerizable vinyl compounds at the polystyrene terminals. In parent nonsubstituted DPE, five functional derivatives possessing electron-donating (N,N-dimethylamino and trialkylsilyloxy) electron-withdrawing (bromo, acyl, cyano) groups were employed in LAAR a living difunctional polystyryl anion. The...

Arsenocholine-containing methacrylate (MTAsB) inspired by marine organisms was synthesized the reaction of 2-bromoethyl and trimethylarsine to investigate its polymerization behavior fundamental properties resulting polymer. Controlled radical MTAsB proceeded in presence a copper catalyst imidazolium chloride at 60 °C for 8 h give water-soluble polycation with 94% yield. The smaller amount nonfreezing water intermediate poly(MTAsB) observed compared that ammonium-containing polycations. A...

This article reviews the successful development of two specially designed linking methodologies in conjunction with a living anionic polymerization system for synthesis novel multiblock polymers, composed three or more blocks, difficult to be synthesized by sequential polymerization. The first methodology use new heterofunctional agent, 2-(4-chloromethylphenyl)ethyldimethylchlorosilane (1), was developed polymers containing poly(dimethylsiloxane) (PDMS) blocks. is based on selective reaction...

A nanostructure consisting of rectangular polyhedral oligomeric silsesquioxane (POSS) nanodomains packed into a hexagonal lattice was observed in POSS-containing A2B star-branched polymers. The polymers, which comprised polystyrene (A) and bulky poly(methacrylate) (PMAPOSS) (B) units, were synthesized by anionic polymerization addition reaction. self-assembled structures the polymers studied via transmission electron microscopy (TEM) small- wide-angle X-ray scattering (SAXS WAXS,...

A new stepwise iterative methodology based on living anionic polymerization using a trifunctional lithium reagent substituted with trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), and tetrahydropyranyl (THP) ethers of protected hydroxyl functionalities has been developed in order to obtain synthetically challenging many-armed μ-star polymers. In each reaction sequence the methodology, these three ether functions were selectively deprotected turn under carefully selected conditions as...

The general utility of a 1,1-diphenylethylene (DPE) derivative substituted with trimethylsilyl- and tert-butyldimethylsilyl-protected hydroxyl functionalities, as new dual-functionalized core agent in conjunction living anionic polymerization system, has been demonstrated by the successful synthesis various well-defined 3-arm ABC 4-arm ABCD μ-star polymers. Two different protected functionalities were progressively deprotected to generate groups, followed conversion α-phenyl acrylate (PA)...

This paper reviews the precise synthesis of architectural polymers by methodologies utilizing either chain-end- or in-chain-functionalized AB diblock copolymers as efficient key building blocks. Architectural herein synthesized are miktoarm star-branched polymers, exact graft copolymers, high-density comblike and alternative sequential multiblock copolymers. Chain-end- and, in some cases, core-functionalized ABC utilized blocks prepared living anionic polymerization conjunction with...