High pressure synthesis of newN,N-diphenyl-pendent aromatic ionene polymers fromN,N,N ′,N ′-tetraphenyl-m-xylylenediamine and aliphatic dihalides

Imai, Yoshio; Shiratori, Motohito; Jikei, Mitsutoshi; Kakimoto, Masa–aki

doi:10.1002/1521-3935(20001101)201:17<2316::aid-macp2316>3.0.co;2-4

Cited by 4 publications

(2 citation statements)

References 10 publications

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“…Thus, it is possible that the ionic groups along the main chain provide additional thermal resistance derived from their strong ionic interactions. However, no decrease in degradation temperature was observed with increasing aliphatic fragment length, a fact commonly observed in several nonionic and ionic polymers [42,43].…”

Section: Thermal Propertiesmentioning

confidence: 74%

Ionenes as Potential Phase Change Materials with Self-Healing Behavior

Arriaza-Echanes,

Velázquez-Tundidor,

Angel-López

et al. 2023

Polymers

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Ionenes are poly(ionic liquids) (PILs) comprising a polymer backbone with ionic groups along the structure. Ionenes as solid–solid phase change materials are a recent research field, and some studies have demonstrated their potential in thermal dissipation into electronic devices. Eight ionenes obtained through Menshutkin reactions were synthesized and characterized. The analysis of the thermal tests allowed understanding of how the thermal properties of the polymers depend on the aliphatic nature of the dihalogenated monomer and the carbon chain length. The TGA studies concluded that the ionenes were thermally stable with T10% above 420 °C. The DSC tests showed that the prepared ionenes presented solid–solid transitions, and no melting temperature was appreciated, which rules out the possibility of solid–liquid transitions. All ionenes were soluble in common polar aprotic solvents. The hydrophilicity of the synthesized ionenes was studied by the contact angle method, and their total surface energy was calculated. Self-healing behavior was preliminarily explored using a selected sample. Our studies show that the prepared ionenes exhibit properties that make them potential candidates for applications as solid–solid phase change materials.

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Section: Thermal Propertiesmentioning

confidence: 74%

Ionenes as Potential Phase Change Materials with Self-Healing Behavior

Arriaza-Echanes,

Velázquez-Tundidor,

Angel-López

et al. 2023

Polymers

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“…There is only one prior literature example of a tetraarylamine of this type, the unsubstituted N,N′- [1,3-phenylenebis(methylene)]bis(Nphenylaniline). 16 However, extremely forcing conditions were required to convert the m-xylylene dichloride to the desired compound. Crystallization from hexanes afforded crystals of suitable quality for study using single-crystal X-ray diffraction experiments.…”

Section: Scope and Limitationsmentioning

confidence: 99%

A Simple and Convenient Method for the Synthesis of N,N-Diaryl Tertiary Amines

et al. 2014

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Direct preparation of tertiary amines in which two substituents are aromatic is described. In the presence of either the inorganic base sodium tert-butoxide or the sterically hindered organic base diisopropylethylamine, the alkylation of secondary diarylamines is achieved smoothly. In contrast to methods previously reported in the literature, this procedure is high-yielding and does not require the use of transition-metal catalysts or functional-group-intolerant hydride reductants.Amines are widely used in the chemical industry as basic intermediates in the preparation of fine chemicals and pharmaceuticals. 1,2 Since amines are common structural features of most naturally occurring biologically active compounds, they have been used in the design of chemotherapeutic approaches to a variety of diseases. 3 Thus, a great deal of sustained research interest in new synthetic approaches to amines has been generated. Specifically, the preparation of tertiary amines (NR 1 R 2 R 3 ) has been approached in a variety of ways, each with unique benefits and drawbacks. Buchwald 4 and Hartwig 5 have shown that the copper-or palladium-catalyzed N-arylation of a variety of amines using aryl halides is a powerful method for the synthesis of arylamines. However, the requirement of a transition-metal catalyst and often-poor yields of tertiary amines are undesirable aspects of this approach. The direct alkylation of secondary amines with alkyl halides is the most straightforward way for the synthesis of tertiary amines. However, formation of quarternary ammonium salts, together with mixtures of starting material and desired tertiary amine limits the general application of this method. 6 Reduction of amides using alkali metal or boron hydrides is another common procedure. However, the use of low functional group tolerant strong inorganic bases coupled with the air and moisture sensitivity of such hydrides complicates their general use. 7 Catalytic hydrogenation of primary and secondary amides to amines has been reported under conditions of high pressures and temperatures, but reductions of tertiary amides via hydrogenations has not been observed. 8 Over the last few years, metal-catalyzed reductions of amides employing silanes have been extensively investigated. Recently, Brookhart reported the use of an iridium pincer complex in the reduction of tertiary amides 9 (Scheme 1). However, the use of a precious metal catalyst and generation of stoichiometric siloxane by-products significantly limit the general use of this approach. Beller and co-workers recently reported an iron-catalyzed reduction procedure. 10 Whereas this method employs an earth-abundant transition metal, an important improvement, stoichiometric amounts of siScheme 1 Selected routes to reduction of amides to tertiary amines O N Ar Ar noble metal catalyst/silanes Brookhart/Beller Charette N H O OEt O EtO Me Me HNAr 2 DIPEA this work R O N Ar Ar R TMS R N Ar Ar R Br R OTf R N Ar Ar HNAr 2 , CsF (2.0 equiv ) Larock SYNTHESIS PSP 270 No Downloaded by: Flinders University of ...

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Main‐chain viologen polymers with organic counterions exhibiting thermotropic liquid‐crystalline and fluorescent properties*

Bhowmik

Han

Cebe

et al. 2002

J. Polym. Sci. A Polym. Chem.

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A series of viologen polymers with bromide, tosylate, and triflimide as counterions were prepared by either the Menshutkin reaction or metathesis reaction in a common organic solvent. Their polyelectrolyte behavior in methanol was determined by solution viscosity measurements, and their chemical structures were determined by Fourier transform infrared and Fourier transform NMR spectroscopy. They were characterized for their thermotropic liquid-crystalline properties with a number of experimental techniques. Each of the viologen polymers with organic counterions had a low melting transition or fusion temperature above which it formed either a highorder smectic phase or a low-order smectic phase. Each of them also exhibited a smectic-to-isotropic transition. The ranges of the liquid-crystalline phase were 80 -88°Cfor viologen polymers with tosylate as a counterion and 120 -146°C for viologen polymers with triflimide as a counterion. They had excellent thermal stability. The ranges of thermal stability were 288 -329°C for viologen polymers with tosylate as a counterion and 343-350°C for viologen polymers with triflimide as a counterion. The fluorescence property for all of the viologen polymers in either aqueous or methanol solution was also included in this study. For example, the viologen polymer containing the 4,4Ј-bipyridinium and p-xylyl units along the backbone of the polymer chain with triflimide as a counterion had an absorption spectrum ( max ϭ 265 nm), an excitation spectrum ( ex values ϭ 357, 443, and 454 with monitoring at 533 nm), and an emission spectrum ( em ϭ 536 nm with excitation at 430 and 450 nm) in methanol.

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High pressure synthesis of newN,N-diphenyl-pendent aromatic ionene polymers fromN,N,N ′,N ′-tetraphenyl-m-xylylenediamine and aliphatic dihalides

Cited by 4 publications

References 10 publications

Ionenes as Potential Phase Change Materials with Self-Healing Behavior

Ionenes as Potential Phase Change Materials with Self-Healing Behavior

A Simple and Convenient Method for the Synthesis of N,N-Diaryl Tertiary Amines

Main‐chain viologen polymers with organic counterions exhibiting thermotropic liquid‐crystalline and fluorescent properties*

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