Polymers 2a Research Articles

Synthesis and photoluminescence properties of poly(1-hexyl-2-aryl acetylene)s, poly(1-phenyl-2-fluorenylacetylene), and poly(1-fluorenyl-2-fluorenlacetylene)

The metathesis polymerizations of 1-hexyl-2-arylacetylenes [ n-C 6H 13C CAr; Ar = phenyl ( 1a), naphthyl ( 1b), biphenyl ( 1c), fluorenyl ( 1d)] were examined using NbCl 5, TaCl 5, and WCl 6. When NbCl 5/ n-Bu 4Sn was used as a catalyst in their polymerization, high-molecular-weight polymers ( 2a– 2d) were obtained in good yield compared to TaCl 5/ n-Bu 4Sn and WCl 6/Ph 4Sn. 1-Hexyl-2-[2-(9,9-dialkylfluorenyl)]acetylenes ( 1e– 1h) also polymerized by NbCl 5/ n-Bu 4Sn to give corresponding polymers ( 2e– 2h) with relatively high molecular weights. Diarylacetylene polymers ( 2i and 2j) were obtained by the metathesis polymerization using TaCl 5/ n-Bu 4Sn. All the poly(1-hexyl-2-arylacetylene)s ( 2a– 2h) emitted blue-colored lights, and the fluorenyl group-containing polymers exhibited strong photoluminescence. However, the fluorenyl group-containing polymers with long alkyl groups such as n-butyl and n-octyl groups at the 9-position on fluorene rings showed weak emissions because the steric hindrance of long alkyl groups prevents to form intramolecular excimers. The emission spectra of diarylacetylene polymers red-shifted, and 1-phenyl-2-[2-(9,9-dimethylfluorenyl)]acetylene ( 2i) and 1-(2-fluorenyl)-2-[2-(9,9-dimethylfluorenyl)]acetylene ( 2j) showed green-colored and yellow-colored emissions, respectively.

Coordination polymers with chelidonate (4-oxo-4 H-pyran-2,6-dicarboxylate) anions and dmso: [Zn(chel)(dmso) 2] and linkage isomers of [Co(chel)(dmso)(OH 2) 3]·H 2O

Recrystallization from dmso of the previously prepared compound [Co(chel)(H 2O) 4] (chel = 4-oxo-4 H-pyran-2,6-dicarboxylate), led to the new one-dimensional coordination polymers 1a and 1b, which are linkage isomers of formula [Co(chel)(dmso)(OH 2) 3]·H 2O. Also the recrystallization from dmso of the previously prepared [Zn(chel)(H 2O) 2] allow the isolation of the one-dimensional coordination polymer [Zn(chel)(dmso) 2] ( 2). [Co(chel)(H 2O) 4] was characterized by elemental analysis, IR and electronic spectroscopy, magnetic measurements at room temperature and thermogravimetric analysis. X-ray single crystal diffraction of 1a, 1b and 2 showed the coordinative behavior of the chelidonate ligand in each compound as well as the different participation of this ligand in the corresponding metallosupramolecular organization.

Low-Bandgap Donor−Acceptor Conjugated Polymer Sensitizers for Dye-Sensitized Solar Cells

A set of two donor-acceptor type conjugated polymers with carboxylic acid side groups have been synthesized and utilized as active materials for dye-sensitized solar cells (DSSCs). The polymers feature a π-conjugated backbone consisting of an electron-poor 2,1,3-benzothiadiazole (BTD, acceptor) unit, alternating with either a thiophene-fluorene-thiophene triad (2a) or a terthiophene (3a) segment as the donor. The donor-acceptor polymers absorb broadly throughout the visible region, with terthiophene-BTD polymer 3a exhibiting an absorption onset at approximately 625 nm corresponding to a ∼1.9 eV bandgap. The polymers adsorb onto the surface of nanostructured TiO(2) due to interaction of the polar carboxylic acid units with the metal oxide surface. The resulting films absorb visible light strongly, and their spectra approximately mirror the polymers' solution absorption. Interestingly, a series of samples of 3a with different molecular weight (M(n)) adsorb to TiO(2) to an extent that varies inversely with M(n). DSSCs that utilize the donor-acceptor polymers as sensitizers were tested using an I(-)/I(3)(-) electrolyte. Importantly, for the set of polymer sensitizers 3a with varying M(n), the DSSC efficiency varies inversely with M(n), a result that reflects the difference in adsorption efficiency observed in the film absorption experiments. The best DSSC cell tested is based on a sample of 3a with M(n) ∼ 4000, and it exhibits a ∼65% peak IPCE with J(sc) ∼12.6 mA cm(-2) under AM1.5 illumination and an overall power conversion efficiency of ∼3%.

Influence of polymer conformations on the aggregation behaviour of alternating dialkylsilylene-[4,4′-divinyl(cyanostilbene)] copolymers

The influence of the substituents at silicon on the aggregation enhanced emission (AEE) of alternating dialkylsilylene-[4,4′-divinyl(cyanostilbene)] copolymers 3 and 4 is examined. The presence of the bulky isopropyl group in 3b significantly enhances the quantum yield upon aggregation. On the other hand, the emission intensity of the methyl-substituted polymer 3a is only slightly enhanced under the same conditions. The bulky isopropyl substituents on silicon may exert the Thorpe–Ingold effect on these copolymers resulting in conformation difference, which may dictate the nature of the aggregation between polymers, and hence, the photophysical behaviour of these polymers.

Conformational supramolecular isomerism in one-dimensional silver(i) coordination polymer of a flexible bis(bidentate) N,N-donor ligand with p-xylyl spacer

The isolation and structural characterisation of three isomeric silver(I) complexes, 1a, 1b and 2 with the general formula {[AgL(1)]ClO(4)}(n) (where L(1) is a bis(bidentate) N,N-donor ligand derived from the Schiff-base condensation of α,α'-diamino-p-xylene and pyridine-2-carboxaldehyde) are discussed. Single-crystal X-ray structures reveal the polymeric nature for the complexes where all the silver ions are in pseudotetrahedral geometry with the AgN(4) coordination environment. Isomers 1a (Pc space group) and 1b (Cc space group) were crystallised from acetonitrile whereas 2 (C2/c space group) was crystallised during the synthesis from a solvent mixture of dicholormethane and methanol. The flexible ligand (L(1)) adopts only an anti conformation in 1b and the presence of two different anti conformations in the repeating unit results in the formation of a trapezoidal wave polymeric chain. However, both gauche and anti conformations of the ligand are found to be present in the polymeric chains of 1a. In the polymeric chain of 2, only one anti isomer of the ligand is present in the repeating unit resulting in a triangular wave chain. The structure of isomer 1a is solvent induced and solvent plays a major role in the crystal packing of this isomer. One-dimensional coordination polymers 1a, 1b and 2 are related to each other as conformational supramolecular isomers. Additionally, two independent polymeric chains parallel to each other: one triangular wave consisting of only an anti conformation and a trapezoidal wave chain consisting of alternate gauche and anti conformations of the ligand are observed in 1a. This is a rare example of two supramolecular isomers present in the same crystal. Six different conformers of the flexible ligand are observed in the crystals of coordination polymers.

Chiral linear polymers bonded alternatively with salen and 1,4-dialkoxybenzene: synthesis and application for Ti-catalyzed asymmetric TMSCN addition to aldehydes

The synthesis of chiral linear polymers 1a– b having salen and 1,4-dioctyloxybenzene as alternate segments has been accomplished. The GPC analysis showed the molecular weights corresponding to ca. 15 ( M w = 10,999, M n = 9165 and PDI = 1.20) repeating units for 1a and ca. 8 ( M w = 8547, M n = 7883 and PDI = 1.08) repeating units for 1b. Polymers 1a– b have been studied with Ti(O i Pr) 4 as a recyclable catalyst for the asymmetric addition of TMSCN to aldehydes while the selectivity of the polymer catalyst is identical to that of the monomer. The reactions are efficient affording the cyanohydrins with up to 88% ee. The selectivity of the polymer based catalyst 9a is found to be the same to that of the monomer 10a. The reaction provides the advantages of simplified product isolation and easy recovery and recyclability of polymer catalyst 9a without any loss of activity or selectivity.

Acceleration effect of N‐allyl group on thermally induced ring‐opening polymerization of 1,3‐benzoxazine

AbstractThermally induced ring‐opening polymerization of monofunctional N‐allyl‐1,3‐benzoxazine 1a was compared with that of N‐(n‐propyl)‐1,3‐benzoxazine 1b to clarify an unexpected effect of allyl group to promote the polymerization, that is, in spite of the comparable bulkiness of allyl group to n‐propyl group, the polymerization of 1a was much faster than that of 1b. Such a difference in polymerization rate was also observed similarly in the comparison of thermally induced polymerization of a bifunctional N‐allyl‐benzoxazine 2a with that of a bifunctional N‐(n‐propyl) analogue 2b. These observations implied a certain contribution of an electron‐rich CC double bond of the N‐ally group to promotion of the ring‐opening reaction of 1,3‐benzoxazine into the corresponding zwitterionic species, which would involve a mechanism to stabilize the cationic part of the zwitterionic species based on “neighboring group participation” of the CC double bond. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

Dinuclear copper(II) complexes of a novel 3-(aminomethyl)naphthoquinone Mannich base: Synthesis, structural, magnetic and electrochemical studies

A novel versatile tridentate 3-(aminomethyl)naphthoquinone proligand, 3-[ N-(2-pyridylmethyl)aminobenzyl]-2-hydroxy-1,4-naphthoquinone ( HL), was obtained from the Mannich reaction of 2-hydroxy-1,4-naphthoquinone (Lawsone) with 2-aminomethylpyridine (amp) and benzaldehyde. The reactions of HL with CuCl 2·2H 2O yielded two novel dinuclear copper(II) complexes, [Cu( L)(H 2O)(μ-Cl)Cu( L)Cl] ( 1b), [CuCl( L)(μ-Cl)Cu(amp)Cl] ( 2) and a polymeric compound, [Cu( L)Cl)] n ( 1a), whose relative yields were sensitive to temperature, reagents concentration and presence of base. The crystalline structures of 1b and 2 were determined by X-ray diffraction studies. The two copper atoms in complex 1b are connected by a single chloro bridge with a Cu⋯Cu separation of 4.1342(8) Å and Cu(1)–Cl(1)–Cu(2) angle of 109.31(4)°. In complex 2 the two copper atoms are held together by a chloro and a naphthalen-2-olate bridges [Cu(1)–Cl(2)–Cu(2) and Cu(1)–O(1)–Cu(2) angles being 83.31(3) and 109.70(9)°, respectively, and the Cu⋯Cu separation, 3.3476(9) Å]. As expected, variable-temperature magnetic susceptibility measurements of complex 1b showed weak antiferromagnetic intramolecular coupling between the copper(II) centers, with J = −5.7 cm −1, and evidenced for complex 2 strong antiferromagnetic coupling, with J ∼ −120 cm −1. Furthermore, the magnetic behaviour of compound 1a suggested an infinite 1D coordination polymeric structure in which the copper(II) centers are connected by Cl–Cu–Cl bridges. Solution data (UV–Vis spectroscopy and cyclic voltammetry) indicated structural changes of 2 and 1a in CH 3CN, and evidenced conversion of polymer 1a into dimer 1b.

Synthesis and characterization of benzocyclobuten-4-yl acrylate monomer and its radical polymerization

A benzocyclobuten-4-yl acrylate (1) monomer was prepared by esterification of 4-hydroxybenzocyclobutene with acryloyl chloride. The radical homopolymerization of 1 and copolymerization of 1 with styrene or n-butyl acrylate were carried out to produce linear polymers 2a, 2b and 2c. Heating of these linear polymers under thermal initiation gave corresponding cross-linked polymers 3a, 3b and 3c. The ring-opening reaction in the cross-linking process was confirmed by on-line infrared spectra. Differential scanning calorimetry showed that the glass transition temperatures of linear polymers 2a and 2b were 83.2°C and 68.1°C, respectively. Thermogravimetric analysis of the cross-linked polymers showed that they all exhibited good thermal stability.

Synthesis of calix[4]arene bearing pyridinium units supported silica gel for sorption of arsenate and dichromate anions

In the present study two new silica gel-immobilized calix[4]arene polymers 4a and 4b have been prepared via modification of calix[4]arene, which contains pyridinium units 3a or 3b with silica-based polymer ( ECHES) and investigated their sorption ability towards arsenate and dichromate anions at different pH. The prepared polymers were characterized by Fourier transform infrared spectroscopy, elemental analysis and thermal gravimetric analysis. Finally, the sorption properties of polymers ( 4a and 4b) towards dichromate and arsenate anions were reported. It was found that these calix[4]arene-based polymers exhibit a high level of sorption abilities towards dichromate and arsenate anions. It was observed that the percentage of arsenate removal reached 62–57% for polymer 4a and 59–50% for 4b when the pH of the aqueous solution was kept in the range of 3.5–4.5. The sorption of arsenate and dichromate anions by calix[4]arenes-based polymers indicates that the partially protonated pyridyl groups play a major role for the formation of hydrogen bonds and electrostatic interactions. In order to fully comprehend the selectivity of 4a, we also examined the retention of dichromate anions in the presence of Cl −, NO 3 − and SO 4 2− anions at pH 1.5.

Polynorbornene with pentafluorophenyl imide side chain groups: Synthesis and sulfonation

AbstractThe mixtures of exo‐endo‐monomers and isomerically pure endo‐monomers of N‐pentafluorophenyl‐norbornene‐5,6‐dicarboximide (2a) and N‐phenyl‐norbornene‐5,6‐dicarboximide (2b) were synthesized and polymerized via ring opening metathesis polymerization using bis(tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride (I) and tricyclohexylphosphine [1,3‐bis(2,4,6‐trimethylphenyl)‐4,5‐dihydroimidazol‐2‐ylidene][benzylidene] ruthenium dichloride (II). Ring opening metathesis polymerization of mixtures of exo‐endo‐monomers (2a) and (2b) and pure endo‐2b gave the corresponding high molecular weights poly(N‐pentafluorophenyl‐norbornene‐5,6‐dicarboximide) (3a) and poly(N‐phenyl‐norbornene‐5,6‐dicarboximide) (3b). The isomerically pure endo‐2a did not polymerize by I in these conditions, since I is the least active catalyst and endo‐2a is the least active monomer because of the intramolecular complex formation between the Ru active center and the fluorine atom of ring‐opened endo‐2a on the one hand and steric hindrances caused by the pentafluorinated ring on the other. The quantitative hydrogenation of the polymer 3a, at room temperature and 115 bar, was achieved by a Wilkinson's catalyst. The new polynorbornene bearing highly fluorinated sulfonic acid groups (5) was obtained by the reaction of the hydrogenated poly(N‐pentafluorophenyl‐norbornene‐5,6‐dicarboximide) (4) with sodium 4‐hydroxybenzenesulfonate dihydrate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2925–2933, 2010

Synthesis and gas permeation properties of various Si-containing poly(diarylacetylene)s and their desilylated membranes

Diarylacetylene monomers having trimethylsilyl groups and other substituents (substituted biphenyl, 1a and 1b; trimethylsilylmethylphenyl, 1c– e) were synthesized and polymerized with TaCl 5- n-Bu 4Sn catalyst to produce the corresponding poly(diarylacetylene)s ( 2a– d). Polymers 2a– c had high molecular weights and were soluble in common organic solvents. Free-standing membranes of 2a– c as well as previously reported 2f– h were prepared by the solution-casting method. Desilylation of these Si-containing polymer membranes was carried out with trifluoroacetic acid to afford 3a, 3b, and 3f– h. Upon desilylation, biphenyl-containing membranes became less permeable ( 3a, b), whereas fluorene-containing membranes became more permeable ( 3f– h). In particular, 3h exhibited extremely high gas permeability ( PO 2 = 9800 barrers), which is about the same as that of poly(1-trimethylsilyl-1-propyne). Desilylated membranes 3a and 3f– h showed different gas permeability from that of polymers 2i– k which have the identical chemical structures and obtained directly by the polymerization of the corresponding monomers.

Hyperbranched Conjugated Polymers: Postfunctionalization

In this contribution, the synthesis of two different hyperbranched poly(phenylene vinylene-phenylene ethynylene) (HB-PPV-PPE, 3a−b) scaffolds are reported. The necessary AB2 monomer 2 is obtained by an asymmetric Horner reaction and contains two iodine substituents and one ethynyl group. This AB2 monomer provides, after Sonogashira polymerization, a hyperbranched conjugated polymer decorated with iodine groups, suitable to be further functionalized with terminal alkynes 4a−t by a Pd-catalyzed coupling. Elemental analysis of the postfunctionalized polymers 5a−t and 6a−q reveals nearly complete substitution of the iodine groups. As a consequence of the replacement, substantial increases in fluorescence quantum yields as well as variation in the optical response of the new polymers are observed. The spectroscopic properties of the postfunctionalized polymers were investigated in solution and in the solid state. The emission of the formed hyperbranched polymers shows a strong dependence on the functional grou...

Synthesis and gas permeation properties of poly(diarylacetylene)s having substituted and twisted biphenyl moieties

Diarylacetylene monomers containing substituted biphenyl (1a–f) and anthryl (1g) groups were synthesized and then polymerized with TaCl5-n-Bu4Sn catalyst to produce the corresponding poly(diarylacetylene)s (2a–g). Polymers 2a–f were soluble in common organic solvents such as cyclohexane, toluene, and chloroform. According to thermogravimetric analysis, the onset temperatures of weight loss of the polymers were over 400 °C in air, indicating considerably high thermal stability. Free-standing membranes 2a and 2c–e were prepared by the solution casting method. Desilylation of Si-containing membrane 2c was carried out with trifluoroacetic acid to afford 3c. All the polymer membranes, especially those having twisted biphenyl groups, exhibited high gas permeability; for example, their oxygen permeability (PO2) values ranged from 130 to 1400 barrers. Membrane 2d having two chlorine atoms in the biphenyl group showed the highest gas permeability (PO2 = 1400 barrers) among the present polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 861–868, 2010

One‐Dimensional Polymers Based on Silver(I) Cations and Organometallic cyclo‐P3 Ligand Complexes

The synthesis and characterization of the first supramolecular aggregates incorporating the organometallic cyclo-P3 ligand complexes [CpRMo(CO)2(eta3-P3)] (CpR=Cp (C5H5; 1a), Cp* (C5(CH3)5; 1b)) as linking units is described. The reaction of the Cp derivative 1a with AgX (X=CF3SO3, Al{OC(CF3)3}4) yields the one-dimensional (1D) coordination polymers [Ag{CpMo(CO)2(mu,eta3:eta1:eta1-P3)}2]n[Al{OC(CF3)3}4]n (2) and [Ag{CpMo(CO)2(mu,eta3:eta1:eta1-P3)}3]n[X]n (X=CF3SO3 (3a), Al{OC(CF3)3}4 (3b)). The solid-state structures of these polymers were revealed by X-ray crystallography and shown to comprise polycationic chains well-separated from the weakly coordinating anions. If AgCF3SO3 is used, polymer 3a is obtained regardless of reactant stoichiometry whereas in the case of Ag[Al{OC(CF3)3}4], reactant stoichiometry plays a decisive role in determining the structure and composition of the resulting product. Moreover, polymers 3a, b are the first examples of homoleptic silver complexes in which Ag(I) centers are found octahedrally coordinated to six phosphorus atoms. The Cp* derivative 1b reacts with Ag[Al{OC(CF3)3}4] to yield the 1D polymer [Ag{Cp*Mo(CO)2(mu,eta3:eta2:eta1-P3)}2]n[Al{OC(CF3)3}4]n (4), the crystal structure of which differs from that of polymer 2 in the coordination mode of the cyclo-P3 ligands: in 2, the Ag+ cations are bridged by the cyclo-P3 ligands in a eta1:eta1 (edge bridging) fashion whereas in 4, they are bridged exclusively in a eta2:eta1 mode (face bridging). Thus, one third of the phosphorus atoms in 2 are not coordinated to silver while in 4, all phosphorus atoms are engaged in coordination with silver. Comprehensive spectroscopic and analytical measurements revealed that the polymers 2, 3a, b, and 4 depolymerize extensively upon dissolution and display dynamic behavior in solution, as evidenced in particular by variable temperature 31P NMR spectroscopy. Solid-state 31P magic angle spinning (MAS) NMR measurements, performed on the polymers 2, 3b, and 4, demonstrated that the polymers 2 and 3b also display dynamic behavior in the solid state at room temperature. The X-ray crystallographic characterisation of 1b is also reported.

Syntheses, Structures, and Luminescence Properties of a Series of LnIII−BaII Heterometal-Organic Frameworks

Ten novel LnIII−BaII heterometal-organic frameworks, {[Ln2Ba2(PDA)5(H2O)12]·mH2O}n (Ln = Pr (1, m = 9); Sm (2, m = 6); PDA = pyridine-2,6-dicarboxylic anion), {[LnBa1.5(PDA)3(H2O)8]·2H2O}n (Ln = Eu (3); Gd (4); Tb (5)), {[Ln4Ba6(PDA)12(H2O)x]·mH2O}n (Ln = Dy (6, x = 27.5, m = 12); Lu (7, x = 27, m = 11.5)), {[Eu4Ba4(PDA)10(H2O)23]·16H2O}n (3a), {[TbBa3(PDA)4(NO3)(H2O)6]·2H2O}n (5a), and {[DyBa1.5(PDA)3(H2O)7]·2H2O}n (6a), have been successfully synthesized under hydrothermal conditions, and the various structures are constructed from 1D chain, 2D layer, to 3D framework. Compounds 1 and 2 exhibit 1D ribbonlike structures. Compounds 3−5 display 2D layers constructed by 1D BaII chains and [Ln(PDA)3] units. Compounds 6 and 7 exhibit complicated 2D structures different from those of 3−5. When the amount of Ba(OH)2 changes during the syntheses of 3, 5, and 6, three novel coordination polymers 3a, 5a, and 6a were obtained. Compound 3a consists of a 1D chain different from those in 1 and 2. Compound 5a displays a 3D framework, which was constructed through the 2D Ba layers and [Tb(PDA)3] linkers. Compound 6a is isostructural to those of 3−5, although synthetic conditions are different from each other. The significant differences in structure from 1 to 7, and from 3a to 6a, may result from the lanthanide contraction effect, whereas the structural divergences between 3 and 3a, 5 and 5a, and 6 and 6a originate from different amounts of Ba(OH)2 in the synthetic process. The luminescence studies of 2, 3, 5, 6, 3a, 5a, and 6a were applied in the solid state at room temperature, showing intense characteristic emission bands of lanthanide ions, and the results reveal that PDA ligand as an “antenna” may effectively sensitize the luminescence of lanthanide ions.

Transfection and intracellular trafficking characteristics for poly(amidoamine)s with pendant primary amine in the delivery of plasmid DNA to bone marrow stromal cells

Poly(amidoamine)s with pendant primary amine (polymer 1a– 1c) were evaluated as in vitro non-viral gene delivery vectors for bone marrow stromal cells (BMSCs). The cytotoxicity of these poly(amidoamine)s, measured by MTT assay, increased with increasing length of side chain, however, they were less toxic than branched polyethylenimine (PEI) 25 kDa. Using pGL-3 and pEGFP-C1 as luciferase gene and green fluorescent protein (GFP) gene, among all polycations including polymer 1a– 1c and PEI, polymer 1b at optimal N/ P ratio showed highest luciferase expression (1.92 × 10 8 RLU/mg protein) as well as percentage of cells expressing GFP (29.01 ± 2.33%). For all polycations, intracellular trafficking of Cy3-labelled plasmid DNA (pDNA) was similar. Fluorescent particles attached to cell membrane at 0.5 h after adding the polycation/DNA complexes, aggregated in cytoplasm after 2 h, and then stayed around the perinuclear region after 4 h. pDNA nuclear localization appeared at 4 h post-transfection, but much more pDNA entered into nucleus at 24 h. At high N/ P ratio, polymer 1a– 1c could deliver pDNA into 70–80% of BMSCs after 24 h transfection, however, labelled pDNA was observed in only 4–25% of cells at the same time. Compared to PEI, polymer 1b showed comparable or even higher percentage of pDNA uptake and nuclear localization. We concluded that poly(amidoamine)s with pendant primary amine, especially polymer 1b, are new kind of promising candidates of less toxic and highly efficient non-viral gene delivery vectors for BMSCs.

The microwave-assisted synthesis and characterization of novel, octakis(2-hydroxyethoxy)resorcinarene bridged polymeric metallophthalocyanines

The new metallophthalocyanine (Zn, Cu, Ni, Co) polymers containing 4,6,10,12,16,18,22,24-octakis(2-hydroxyethoxy)-2,8,14,20-tetramethylresorcinarene are described. Firstly, 4,6,10,12,16,18,22,24-octakis(2-hydroxyethoxy)-2,8,14,20-tetramethylresorcinarene compound ( 1) was synthesized by treating resorcinarene with 2-chloroethanol under microwave irradiation. Then, tetrakis(4,5-bis(2-hydroxyethoxy))phthalonitrile substituted resorcinarene compound ( 2) and octakis(4-(2-hydroxyethoxy))phthalonitrile substituted resorcinarene compound ( 3) were synthesized by treating compound ( 1) with 4,5-dichloro-1,2-dicyanobenzene and 4-nitro-1,2-dicyanobenzene, respectively, under microwave irradiation. The chlorides Cu (II), Ni (II), Co (II), were employed in order to synthesize the corresponding metallophthalocyanine polymers ( 2b– d and 3b– d) and Zn(CH 3COO) 2 was used for the preparation of zinc phthalocyanine polymers ( 2a and 3a). All products were synthesized by microwave-assisted synthesis method. The structures were characterized by elemental analyses, 1H NMR, 13C NMR, UV–Vis and FTIR spectroscopy.

Synthesis of PEG‐functionalized poly(diphenylacetylene)s and their gas permeation properties

AbstractThe polymerizations of 1‐(3‐methylphenyl)‐2‐(4‐trimethylsilyl)phenylacetylene (1a) and 1‐(4‐methylphenyl)‐2‐(4‐trimethylsilyl)phenylacetylene (1b) were carried out with TaCl5‐n‐Bu4Sn to give relatively high‐molecular‐weight polymers (2a and 2b) (Mn > 5 × 105). The obtained polymers were brominated by using benzoyl peroxide and N‐bromosuccinimide first, followed by substitution reaction of three types of polyethylene glycol. When diethylene glycol was used as a reagent on substitution reaction of meta‐substituted polymer, PEG‐functionalized poly(diphenylacetylene) with the highest content of oxyethylene unit [4a(2)] was obtained, and the degree of substitution was 0.60. The degrees of substitution decreased to 0.15 and 0.08 when the polyethylene glycols with higher molecular weights were used. PEG‐substitution reaction to the para‐substituted polymers was difficult to proceed, and hence the degree of substitution was 0.18 even when diethylene glycol was used. The CO2/N2 separation factor of PEG‐functionalized polymer [4a(2)] was as large as 28.8, although that of 2a was 7.41. The other PEG‐functionalized polymers also exhibited high CO2 permselectivity, and their CO2/N2 separation factors were over 20. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Membranes from Poly(aryl ether)-Based Ionomers Containing Randomly Distributed Nanoclusters of 6 or 12 Sulfonic Acid Groups

We report on the dependence of the properties on the morphologies of sulfonated polymers 3a and 3b (ηinh = 0.65−1.18) with segments containing clusters of 6 and 12 sulfonic acid groups, respectively. The larger sulfonated clusters in polymers 3b resulted in higher proton conductivity and much better cell performance than polymers 3a. The highest power density of a fuel cell using 3a-1 (IEC = 1.16 mequiv/g) and Nafion 117 was 0.23 and 0.21 W/cm2, respectively, at the effective work potential of 0.5 V, whereas that of 3b-1 (IEC = 1.16 mequiv/g) was 0.29 W/cm2 at even higher effective work potential of 0.6 V. The morphological structure of 3a-1 and 3b-1 was investigated by transmission electron microscopy (TEM) and compared with that of Nafion. TEM images of 3a-1 and 3b-1 revealed a phase separation similar to that of Nafion, which may explain their higher proton conductivities compared to those of randomly sulfonated copolymers.