Structural characterization of the new polymorphic mesophases formed by bent-core molecules

A new achiral banana-shaped five-ring 2-methylresorcinol derivative fluorinated on the outer rings has been synthesized. This compound exhibits four antiferroelectric smectic phases characteristic for bent-core molecules (B 2 , B' 2 , B' 2 , B 5 ). In addition, a highly viscous solid-like phase has been detected which also shows electro-optical switching. This is the first switchable highly ordered B phase. The characterization of the mesophases was made by X-ray diffraction, electro-optical measurements and dielectric spectroscopy.     

New azobenzene containing bent-core liquid crystals based on disubstituted resorcinol

New bent-core molecules with 4,6-dichlororesorcinol or 4-chloro-2-methylresorcinol as the central unit, and azobenzene with different alkyloxy chain length as side arms were synthesised. The mesophase behaviour of the new compounds was investigated by polarising optical microscopy, differential scanning calorimetry, X-ray diffraction studies and electro-optical measurements. It is found that 4,6-dichlororesorcinol is more conducive towards mesomorphism than 4-chloro-2-methylresorcinol. The liquid crystalline properties of all of the prepared compounds are greatly affected by the lateral substitution on the outer ring. 4,6-Dichlororesorcinol-based compounds without lateral substitution show nematic phases with cybotactic cluster of the SmC-type (N_CybC). Moreover, depending on the chain length, the nematic phase appears as enantiotropic phase for the shortest homologue and as monotropic phase for the higher homologues.     

Rheological and rheokinetic properties of phosphazene-containing epoxy oligomers

The rheological and rheokinetic properties of a two-component binder consisting of epoxy-diane oligomers and the oligoepoxyphosphazenes PEO-1 (30 wt %) and PEO-2 (40 wt %) are studied. The viscosities of the initial oligomers at 40°C are 130 (PEO-1) and 270 (PEO-2) Pa s; the activation energies of viscous flow in the range 40–70°C are from 122 to 128 kJ/mol. The addition of equivalent amounts of curing agents, such as triethylenetetramine or iso-methyltetrahydrophthalic anhydride, reduces the initial viscosity of a composition, most strongly in the presence of the second curing agent (by a factor of 50–100). The activation energies of the cure process with triethylenetetramine in the range 45–95°C are 89 (PEO-1) and 125 (PEO-2) kJ/mol, and the gelation time at 55°C is 6 min for both oligomers. The time of gelation for the system PEO–iso-methyltetrahydrophthalic anhydride at 90°C is 475 min, and the glass-transition temperatures of the cured compositions are 238 (PEO-1) and 250°C (PEO-2), as evidenced by thermomechanical studies.     

Ethylene Polymerization-Induced Self-Assembly (PISA) of Poly(ethylene oxide)-block-polyethylene Copolymers via RAFT

Poly(ethylene oxide) (PEO) with dithiocarbamate chain ends (PEO–SC(=S)−N(CH₃)Ph and PEO–SC(=S)−NPh₂, named PEO-1 and PEO-2 , respectively) were used as macromolecular chain-transfer agents (macro-CTAs) to mediate the reversible addition–fragmentation chain transfer (RAFT) polymerization of ethylene in dimethyl carbonate (DMC) under relatively mild conditions (80 °C, 80 bar). While only a slow consumption of PEO-1 was observed, the rapid consumption of PEO-2 led to a clean chain extension and the formation of a polyethylene (PE) segment. Upon polymerization, the resulting block copolymers PEO-b-PE self-assembled into nanometric objects according to a polymerization-induced self-assembly (PISA).     

Multi-step sol-gel process and its effect on the morphology of polyethylene oxide (PEO)/SiO2 anion-exchange hybrid materials

Polyethylene oxide (PEO)/SiO₂ anion-exchange hybrid materials were prepared through the sol-gel process of alkoxysilane functionalized PEO-1000 (PEO-[Si(OCH₃)₃]₂) and N-[3-(trimethoxysilyl)propyl] ethylene diamine (A-1120). The influence of the multi-step sol-gel processing procedure, i.e. the pre-hydrolysis of either of the two precursors on the homogeneity of the hybrid materials was investigated. Results showed that the sol-gel reaction of A-1120 and PEO-[Si(OCH₃)₃]₂ from the same time would result in hybrid materials with the highest homogeneity, and pre-hydrolysis of A-1120 or PEO-[Si(OCH₃)₃]₂ could only decrease the materials’ compatibility.     

Chain-length dependence of diblock copolymer micellization kinetics studied by stopped-flow pH-jump

A series of well-defined poly(ethylene oxide)- b-poly(2-(diethylamino)ethyl methacrylate) (PEO- b-PDEA) diblock copolymers containing PEO block of identical chain length and PDEA block with varying degrees of polymerization (DP, in the range of 32-154) were prepared via atom transfer radical polymerization (ATRP) employing a PEO-based macroinitiator (DP = 113). Upon a pH-jump from 3 to 12 under highly efficient stopped-flow mixing conditions, PEO- b-PDEA copolymers spontaneously form spherical micelles of increasing sizes and aggregation numbers ( N agg) with increasing PDEA chain lengths. Stopped-flow light scattering technique was used to probe the pH-induced micellization kinetics of PEO- b-PDEA copolymers, aiming to elucidate the PDEA chain-length effects on the unimer-to-micelle transition process. Upon a stopped-flow pH-jump from 3 to 12, the obtained dynamic traces can be well-fitted with double exponential functions. The calculated fast and slow characteristic relaxation times (tau 1 and tau 2) can be ascribed to the formation of quasi-equilibrium micelles (fast process) and subsequent relaxation into final equilibrium micelles (slow process), respectively. For PEO 113- b-PDEA 32 and PEO 113- b-PDEA 61, tau 2 is almost independent of polymer concentrations, suggesting that the relaxation from quasi-equilibrium micelles into final equilibrium micelles mainly proceeds via insertion/expulsion of unimer chains. Upon increasing the DP of pH-responsive PDEA block to 89, 117, and 154, the obtained slow relaxation time, tau 2, tends to decrease with increasing polymer concentrations, suggesting that the slow process is dominated by the micelle fusion/fission mechanism. The apparent activation energy ( E a) associated with tau 2 has also been determined from temperature-dependent micellization kinetics for five PEO- b-PDEA copolymers. It was found that during micellization, copolymers with longer PDEA blocks exhibit much lower E a compared to those with shorter blocks. Thus, we observed experimentally for the first time that increasing the hydrophobic block length in double hydrophilic block copolymers (DHBCs) can transform the mechanism of the slow process from unimer insertion/expulsion to micelle fusion/fission.     

以PEO为基质的离子及质子导电聚合物电解质

本文以PEO-LiClO₄为基质,在其中加入适量的纳米氧化锌及氧化锡,制备PEO-LiClO₄-ZnO及PEO-LiClO₄-SnO₂离子导电聚合物电解质膜,测定了复合电解质膜的电导率,并探讨了纳米粒子与PEO链的相互作用,提出复合电解质膜的电导率提高的主要影响因素。本文还合成以PEO为基质的PEO-12-钨硅酸质子导电聚合物电解质膜,讨论12-钨硅酸的加入对PEO的构型及Keggin离子的影响并分析PEO-12-钨硅     

The structure of grifolin, an antibiotic from a basidiomycete

Structure of grifolin was deduced as 2-trans,trans-farnesyl-5-methylresorcinol (I).     

PEO-12-钨磷酸质子导电聚合物电解质膜

以聚氧乙烯(PEO)为基质, 在其中掺杂适量的钨磷酸, 制备PEO-H₃PW₁₂O₄₀质子导电聚合物电解质膜. XRD及IR测试表明体系中Keggin阴离子与PEO链相互作用形成新的化合物; Keggin阴离子的存在有利于水合质子的形成. PEO-H₃PW₁₂O₄₀复合膜的电导率室温最高可达4.0×10^－3 S•cm^－1.     

Reaction of resorcinol and its derivatives with urea acetals

Reaction of 2-methylresorcinol and pyrogallol with urea acetals of various structures was studied. Depending on the structure of the acetal used, reaction was established to result in eiter calix[4]resorcinols containing urea fragment or in imidazolidin-2-one derivatives.     

Synthesis of Macroheterocycles by Reaction of N,N′-(1,4-Phenylene)bis[N′-(4,4-diethoxybutyl)urea] with Resorcinol and Its Derivatives

An efficient procedure has been developed for the synthesis of macroheterocycles by acid-catalyzed reaction of N,N′-(1,4-phenylene)bis[N′-(4,4-diethoxybutyl)urea] with resorcinol, 2-methylresorcinol, and pyrogallol. The structure of the isolated compounds was proved by spectral methods.

     

Preparation of tripyrrane analogues from resorcinol and 2-methylresorcinol for applications in the synthesis of new benziporphyrin systems

Acid catalyzed condensation of resorcinol or 2-methylresorcinol with 2 equiv. of an acetoxymethylpyrrole gave bis(pyrrolylmethyl)benzene derivatives in moderate yields; these afforded a series of novel aromatic benziporphyrins using the MacDonald "3 + 1" methodology.     

Synthesis of novel 2-arylpyrrolidines by the reaction of 1-(4,4-diethoxybutyl)urea with resorcinols

Reaction of 1-(4,4-diethoxybutyl)urea with resorcinol, 2-methylresorcinol and pyrogallol in chloroform in the presence of trifluoroacetic acid affords new 2,2′-(1,3-phenylene)-bis(pyrrolidine-1-carboxamides).     

Reactions of trialkyl(aryl)phosphonium-substituted acetals with resorcinol and its derivatives

The reactions of 2-tributylphosphonioacetaldehyde acetal with resorcinol and 2-methylresorcinol in an acidic aqueous-ethanol medium afford calix[4]resorcinols containing four tributylphosphonium groups at the lower rim. The corresponding reactions of the triphenylphosphonium analog give phosphonium salts containing the 2,2-diarylethyl moiety.     

Synthesis of aromatic dicarbaporphyrinoids from resorcinol and 2-methylresorcinol

23-Carba-oxybenziporphyrins, a new group of dicarbaporphyrinoids, are easily prepared by reacting tripyrrane analogues derived from resorcinol or 2-methylresorcinol with an indene dialdehyde under MacDonald ‘3+1’ conditions.     

Synthesis of imidazolidinone containing an ammonium nitrogen atom in the ring

The reaction of 1-(2,2-dimethoxyethyl)-1,3,3-trimethylurea with 2-methylresorcinol in dioxane in the presence of trifluoromethanesulfonic acid affords a new type of imidazolidin-2-ones, viz., 5-(2,4-dihydroxy-3-methylphenyl)-1,1,3-trimethyl-2-oxoimidazolidinium triflate containing an endocyclic ammonium nitrogen atom.     

THERMOPLASTIC ELASTOMERS. II. POLY(ETHER-ESTER-IMIDE)S BASED ON 1,4-DIAMINOBUTANE,TRIMELLITIC ANHYDRIDE, 1,4-DIHYDROXYBUTANE,AND POLY(ETHYLENE OXIDE)S

A series of new poly(ether-ester-imide)s, PEEIs, was prepared from an imide dicarboxylic acid based on 1,4-diaminobutane and trimellitic anhydride. This imide dicarboxylic acid polycondensed with 1,4-dihydroxybutane formed the hard segments and poly(ethylene oxide), PEO-1000, or mixtures of PEO-1000 and poly(tetramethylene oxide), PTMO-1000, were used as soft segments. Whenever PTMO-1000 was used as comonomer, macrophase separation was observed at the end of the polycondensation. However, this macrophase separation had little influence on the mechanical properties. A poly(ether-esterimide), PEEI, containing neat PEO-1000 was characterized by dynamic mechanical thermoanalysis, stress-strain and hysteresis measurements, and by melt rheology. The mechanical properties were compared with those of an analogous PEEI containing neat PTMO-1000 and with those of a poly(ether-ester), PEE, based on poly(butylene terephthalate) hard segments and PTMO-1000.     

Calix[4]resorcinols bearing γ-aminoacetal groups on the upper rim. Synthesis and properties

Synthesis of new calix[4]resorcinol molecules with acetal groups on the upper rim associated with calixarene skeleton through γ-aminoalkyl spacers was performed. The condensation of the compounds studied with 2-methylresorcinol was studied.     

β- and γ-amino acetals containing phosphine oxide groups. Synthesis and reactions with resorcinol derivatives

New β- and γ-amino acetals containing phosphine oxide groups were synthesized by the Kabachnik-Fields reaction of β- and γ-amino acetals with paraformaldehyde and dialkylphosphine oxides. Heating of the resulting β- and γ-amino acetals with 2-methylresorcinol and pyrogallol in boiling trifluoroacetic acid afforded (dialkylphosphoryl)(ω,ω-diarylalkyl)ammonium trifluoromethanesulfonates.     

Shape and size mimicry in the design of ternary molecular solids: towards a robust strategy for crystal engineering

2- and 5-methylresorcinol form co-crystals with 4,4'-bipyridine in which some of the bipyridine molecules are loosely bound. These molecules can be replaced with other molecules of a similar shape and size to give a general method for the engineering of a ternary co-crystal.