Synthesis and properties of poly(oxyethylene)s containing thioether,sulfoxide, or sulfone groups

Poly[oxy(ethylthiomethyl)ethylene] (ETE) was prepared from poly[oxy (chloromethyl)ethylene] (CE) by reaction with sodium ethanethiolate. Sulfoxide and sulfone analogues were synthesized by oxidation of the poly[oxy(ethylthiomethyl)ethylene]. By changing the chloromethyl/sodium ethanethiolate ratio, poly[oxy (chloromethyl)ethylene-co-oxy(ethylthiomethyl)ethylene] (CE-ETEs) were easily made. Poly[oxy(ethylsulfinylmethyl)ethylene] (ESXE), poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfinylmethyl)ethylene] (CE-ESXEs), poly[oxy(ethylsulfonylmethyl)ethylene] (ESE), and poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfonylmethyl)ethylene] (CE-ESEs) were obtained by oxidation of ETE or CE-ETEs. There was little if any chain degradation. The (co)polymer structures were confirmed by FTIR and ¹H-NMR spectroscopic studies. Their thermal properties were studied by DSC and TGA. T_gs of ETE, ESXE, and ESE were -57, 36, and 57°C, respectively, and T_d,os (initial decomposition temperature, TGA) were 331, 198, and 308°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 793–801, 1998     

Synthesis,geometric structure,and properties of poly(phenylacetylenes) with bulky para-substituents

Phenylacetylenes (PAs) with bulky substituents (adamantyl, tert-butyl, and n-butyl groups) at the para-position polymerized in good yields with Fe, Rh, Mo, and W catalysts. The formed polymers were soluble, and their number-average molecular weights were in the range of thousands to hundred thousands. Whereas it is known that the poly(PA) obtained with the Fe catalyst is an insoluble cis-cisoidal polymer, the present polymers formed with the same catalyst were totally soluble in many solvents such as benzene and CHCl₃. The ¹H- and ¹³C-NMR and DSC data revealed that both of the polymers formed with the Fe and Rh catalysts had virtually all-cis structures, while those with the Mo and W catalysts had cis-rich and trans-rich structures, respectively. Cis-cisoidal and cis-transoidal structures of para-substituted poly(PAs) could not be distinguished because of their good solubility. The bulky substituents raised the temperature of cis–trans isomerization and improved the thermal stability of the polymers. Poly(p-t-BuPA) showed gas permeability higher than that of poly(PA). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3157–3163, 1998     

Synthesis and electronic properties of poly (E,E)-[6.2]-(2,5) thiophenophane-1,5-diene)

Cationic cyclopolymerization of (E, E)-[6.2]-(2,5) thiophenophane-1,5-diene ( 2 ) gave polymer 3 which has bridged thiophene rings pendant to the polymer backbone. The structural, thermal, and electronic properties of polymer 3 were compared to those of its benzene analogue ( 1 ) and its nonbridged analogue poly (2-vinylthiophene) ( 5 ). The onsets of thermal degradation for polymers 3 and 5 under helium were 425 and 382°C, respectively. Polymer 3 exhibited conductivity in the 10^?3?10^?4 S/cm range when exposed to iodine vapor, four orders of magnitude higher than for 5 treated in the same manner. Apparent energies of activation for conductivity in iodine saturated polymers 3 (0.57 eV) and 5 (0.61 eV) were calculated from conductivity temperature dependence measurements. Conductivity parameters for iodine saturated 3 show both a higher level of conductivity and weaker temperature dependence than for the corresponding cyclopolymer 1 which has benzene rather than thiophene moieties, suggesting that greater charge generation occurs in 3 , due to the lower oxidation potential of the thiophenophane repeat units. Differences in conductivity behavior for iodine saturated polymers 1, 3 , and 5 are discussed in terms of both charge generation and mobility. © 1994 John Wiley & Sons, Inc.     

高分子量PPV的合成、掺杂及导电性

高分子量的聚对苯乙炔（ＰＰＶ）是从单体１．４一二氯甲基苯合成,后者聚合产生水溶性铳盐,此时,对于ＰＰＶ的转换可用二甲硫醚和盐酸的热消除反应,从水溶液中成膜。用ＩＲ、ＵＶ－Ｖｉｓ、ＴＧＡ分析研究了消除反应。ＰＰＶ膜具有良好的机械性能,而且可能是由于ｎ－和ｐ－型杂质得到的材料具有的导电性近似于这些高掺杂聚乙炔。中间聚电解质的转换率对于ＰＰＶ可能是一种调整,并且这些掺杂膜的导电性,可能与平均共轭长度有关     

Synthesis of polyacetylene with sulfoxide functions

Polyacetylene functionalized by sulfoxide groups was synthesized from poly(methyl vinyl sulfoxide) by the elimination of methanesulfenic acid under the action of a strong base at 20—50 °C.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 774–776, March, 2005.     

Poole-Frenkel effect in amorphous poly(p-phenylene sulfide)

The conductivity of poly(p-phenylene sulfide) (PPS) amorphous samples sandwiched between metallic electrodes has been studied as a function of applied voltage, temperature, and electrode material. The voltage (U) dependence of the currents for electric fields within the range 10³–10⁶ V/cm exhibits exp βU^1/2 behavior with β = β_Schottky below the glass transition temperature (T_g ≊ 90°C), and β = β_{Poole-Frenkel} above T_g. Coordinated temperature measurements of dc currents with different metallic contacts and thermally stimulated currents (TSC) indicate, however, that the conductivity at T < T_g is consistent with the so-called “anomalous” Poole-Frenkel effect rather than the Schottky effect. Consequently, the p-type conductivity in amorphous PPS is proposed to be a bulk-limited process due to ionization of two different types of acceptor centers in the presence of neutral hole traps. © 1996 John Wiley & Sons, Inc.     

Transition metal compatibilization of poly(vinylamine) and poly(ethylene imine)

Poly(vinylamine), PVA, complexes with cobalt chloride hexahydrate exhibit a 45 °C enhancement in the glass‐transition temperature per mol % of the d‐block metal cation. Poly(ethylene imine), PEI, complexes with CoCl₂(H₂O)₆ exhibit a 20 °C enhancement in T_g per mol % Co²⁺. Since the basicities of primary and secondary amines are comparable (i.e., pK_b,PVA ≈ 3.34 vs. pK_b,PEI ≈ 3.27) and the rates at which each polymeric ligand displaces waters of hydration in the coordination sphere of Co²⁺ are similar, transition metal compatibilization is operative in blends of both polymers with CoCl₂(H₂O)₆. These two polymers are immiscible in the absence of the inorganic component. Infrared spectroscopy suggests that nitrogen lone pairs in PVA and PEI coordinate to Co²⁺. The stress–strain response of a 75/25 blend of PVA and PEI with 2 mol % Co²⁺ reveals a decrease in elastic modulus from 4.4 × 10⁹ N/m² to 5.7 × 10⁷ N/m², a decrease in fracture stress from 3.7 × 10⁷ N/m² to 2.0 × 10⁶ N/m², and an increase in ultimate strain from 1.3 to 12% relative to the 75/25 immiscible polymer–polymer blend. A plausible explanation for this effect is based on the fact that cobalt chloride hexahydrate compatibilizes both polymers by forming a coordination bridge between nitrogen lone pairs in dissimilar chains. Hence, poly(ethylene imine), which is very weak with a T_g near −40 °C, is integrated into a homogeneous structure with poly(vinylamine) and the mechanical properties of the individual polymers are averaged in the compatibilized ternary complex. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 552–561, 2000     

Preparation and thermal properties of asymmetrically substituted poly(silylenemethylene)s

Poly(silylenemethylene)s of the types [SiMeRCH₂]_n and [SiHRCH₂]_n were prepared by the ring-opening polymerization (ROP) of 1,3-disilacyclobutanes (DSCBs) containing n-alkyl substituents, such as C₂H₅, n-C₃H₇, n-C₄H₉, n-C₅H₁₁, and n-C₆H₁₃, or a phenyl group on the Si. These new polymers include a monosilicon analog of poly(styrene), [SiHPhCH₂]_n. Improved synthesis routes to the DSCB monomers were developed which proceed through Grignard ring closure reactions on alkoxy-substituted chlorocarbosilanes. All of these asymmetrically substituted polymers were obtained in high molecular weight form, except for [SiHPhCH₂]_n. The configurations of all of the polymers were found to be atactic. The aryl-substituted polymers have higher glass transition temperatures (T_gs) and thermal stability than those of the alkyl-substituted poly(silylenemethylene)s. Unlike the polyolefins of the type [C(H)(R)CH₂]_n, where T_g drops continuously from R = Me to n-Hex, the T_gs of the n-C_nH_2n+1 (n = 2–6)-substituted [SiMeRCH₂]_n PSM's appear to reach a maximum (at −61°C) for the R = n-Pr-substituted polymer. Moreover, where it was possible to make direct comparisons among similarly substituted atactic polymers, all of the poly(silylenemethylene)s were found to have lower T_gs than their all-carbon analogs. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3193–3205, 1997     

Preparation and properties of poly(dimethysilyleneethynylenephenylene‐ethynylene)/graphene Composites

Polymer composites with carbon‐based nano‐fillers have generated significant interest in industry and science because of their multifunctional and valuable properties. An APA‐functionalized GO nanofiller (GO–APA) was prepared through the reaction between graphene oxide (GO) and 3‐aminophenyl acetylene (APA) in dimethylformide (DMF) with ammonia hydroxide. Furthermore the PDSEPE/GO–APA composites were made from Poly(dimethysilyleneethynylenephenylene ethynylene) (PDSEPE) and GO–APA. FT‐IR, XRD, XPS, SEM, DSC and TGA techniques were used to characterize the chemical compositions and physical and chemical properties of GO–APA and PDSEPE/GO–APA composites. As a result, the prepared PDSEPE/GO–APA composites show high thermal stabilities, excellent electrical conductivity and good flexural strength. When the weight percentage of GO–APA reaches 0.5%, the PDSEPE/GO–APA composite electrical conductivity increases by 6 orders of magnitude and the flexural strength improves by nearly 33% compared with that of cured PDSEPE resin. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and properties of germanium-containing poly(diphenylacetylenes)

1-Phenyl-2-[m-(trimethylgermyl)phenyl]acetylene (m-Me₃GeDPA) and 1-phenyl-2-[p-(trimethylgermyl)phenyl]acetylene (p-Me₃GeDPA) polymerized with TaCl₅–cocatalyst systems to provide in high yields new polymers having weight-average molecular weights over 1 × 10⁶. Poly(m-Me₃GeDPA) was a yellow solid, which completely dissolved in toluene, chloroform, etc., to form a tough film by solution casting. Poly(p-Me₃GeDPA) was also a yellow solid and partly insoluble in any solvents. The onset temperatures of weight loss for these polymers in the thermogravimetric analysis in air were as high as ca. 400°C. The oxygen permeability coefficient of poly(m-Me₃GeDPA) was 1100 barrers (25°C), which is about twice that of poly(dimethylsiloxane). © 1996 John Wiley & Sons, Inc.     

Rheological properties of solutions of general‐purpose poly(vinyl alcohol) in dimethyl sulfoxide

The characteristic rheological responses of solutions of atactic poly(vinyl alcohol) (PVA) in dimethyl sulfoxide were investigated in terms of the concentration and molecular weight. The syndiotactic dyad content and weight‐average molecular weight of PVA were 52% and 85,000–186,000, respectively. On a modified Cole–Cole plot, the solutions did not give a single master curve with a slope of 2 but gave various curves with slopes of less than 2. Furthermore, the slope slightly decreased with increasing concentration. The deviation from the master curve indicated that the solutions were rheologically heterogeneous, despite optical transparency. Among the PVA solutions, the 14 wt % solutions exhibited very unusual rheological behavior. The loss tangent changed with the shear rate and produced three distinct regions, which indicated a shear‐induced phase transition. With respect to Winter's view on gelation, the 14 wt % solutions underwent a double sol–gel transition as the shear rate increased over the frequency range of 0.05–500 rad/s. However, the molecular weight did not have such noticeable effects on the rheological behavior over the concentration range of 10–14 wt %. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1451–1456, 2004     

Synthesis and properties of poly(1‐naphthylacetylene) and poly(9‐anthrylacetylene)

Polymerizations of 1‐naphthylacetylene (1‐NA) and 9‐anthrylacetylene (9‐AA) by various transition metal catalysts were studied, and properties of the polymers were clarified. 1‐NA polymerized with WCl₆‐based catalysts to offer dark purple polymers in good yield. Especially, a binary catalyst composed of WCl₆ and Ph₃Bi gave a polymer with high molecular weight (M_w = 140×10³) and sufficient solubility in common solvents. The use of Mo and Rh catalysts, in contrast, resulted in the formation of insoluble red poly(1‐NA)s. 9‐AA gave insoluble polymers by both WCl₆‐ and MoCl₅‐based catalysts in moderate to good yields. Copolymerization of 9‐AA with 1‐NA by WCl₆–Ph₃Bi provided a soluble copolymer which exhibited the largest third‐order nonlinear optical susceptibilities (χ⁽³⁾(−3ω; ω, ω, ω) = 40×10⁻¹²) among all the substituted polyacetylenes synthesized so far. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 277–282, 1999     

Synthesis,characterization, and polychelatogenic properties of poly(acrylic acid-co-acrylamide)

The radical copolymerization of acrylic acid with acrylamide was carried out at different monomer ratios in solution (DMF) at 60°C. The corresponding homopolymers were also synthesized to compare their metal ion binding abilities. All the copolymers were characterized by elemental analysis. The metal ion binding properties of these water-soluble polymers with Cu(II), Co(II), Ni(II), Cd(II), Zn(II), Pb(II), Hg(II), Fe(III), and Cr(III) ions were investigated in aqueous solution using the Liquid-Phase Polymer-Based Retention (LPR) technique. Poly(acrylic acid-co-acrylamide) showed a higher retention compared to the homopolymers for all the metal ions except of Hg(II), which was not retained. Besides, the retention of Cd(II) is higher than that an addition of the retention of both homopolymers. It may be attributed to a synergic effect. Maximum capacity for Cu(II) at pH 5.0 was determined to be 1 mmol g⁻¹ (63.5 mg g⁻¹). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2461–2467, 1997     

Electrical conductivity of poly(vinyl chloride) obtained by photodehydrochlorination from laminated poly(vinyl chloride)/polypyrrole films

Poly(vinyl chloride) (PVC) has been converted to an electrically conductive structure by combined electrochemical and photochemical methods. PVC was cast on a polypyrrole (PPy) film electrode which had been electrochemically prepared. The PVC layer in the laminated PVC/PPy films was first dehydrochlorinated under the illumination of UV light, and the generated polyenes were subsequently doped with I₂ and FeCl₃. The maximum electrical conductivity achieved for such PVC film was 2.51 X 10^?2 and 8.63 10^?2 S cm^?1 after I₂ and FeCl₃ doping, respectively. The temperature dependence of the electrical conductivity showed different behavior in higher and lower temperature ranges. In the former (T > 243 K), the T^?1 law held, and the activation energy and bandgap were estimated as 0.25 and 0.49 eV, respectively. In the latter (T < 243 K), the conductivity mechanism followed the variable range hopping model (T^?1/4 law) in which the radius of the localized state wave function and the density of the localized states at the Fermi level were 1.25 × 10³ Å and 1.03 X 10¹⁵ eV^?1 cm^?3, respectively. © 1995 John Wiley & Sons, Inc.     

Novel preparation of electrically conducting poly (vinyl chloride) by photo-dehydrochlorination from poly (vinyl chloride)/polypyrrole composite film

Polypyrrole (PPy) was deposited electrochemically on a platinum plate from a nitric acid solution of pyrrole. The PVC/PPy composite film was finally obtained by casting poly(vinyl chloride) (PVC) onto the PPy electrode from a tetrahydrofuran solution of PVC. The prepared composite film was irradiated at 90°C with a low-pressure mercury lamp in the stream of hydrogen gas saturated with steam, and the PVC film was dehydrochlorinated, leading to the formation of conjugated polyene. The electrical conductivity (σ) of the PVC film in the irradiated composite film was reveled: σ=2.51 × 10^?5S cm^?1. By iodine doping, σ was further enhanced up to 5.04 X 10^?3 S cm^?1. The tensile strength of the irradiated composite film became larger than that of the original PVC film; i.e., the stress at break was: 461 (composite film); 401 kg cm^?2 (PVC). These results were brought about by the doping of radical species to the conjugated polyene. The anion, NO^?₃, doped during the electrodeposition of PPy was photodecomposed to generate radical NO₂ and this species was doped to the polyene, resulting in the formation of electrically conductive PVC and mechanically improved composite film. © 1994 John Wiley & Sons, Inc.     

Synthesis and properties of poly (diphenylacetylenes) having aliphatic para-substituents

1-(p-t-Butylphenyl)-2-phenylacetylene and 1-(p-n-butylphenyl)-2-phenylacetylene were polymerized in catalytic systems based on TaCl₅ to give new polymers in high yields. These monomers were more reactive than diphenylacetylene (DPA) in copolymerization. Unlike poly (DPA), the present polymers were soluble in toluene, CHCl₃, etc. owing to the high configurational entropy induced by the para-substituents. Their relative weight-average molecular weights determined by GPC were in the range of 6 × 10⁵–36 × 10⁵, and films could be obtained by solution casting. These polymers were fairly thermally stable, as seen from their high onset temperatures (320–380°C) of weight loss in TGA in air. The oxygen permeability coefficient of the polymer with t-Bu group was 1100 barrers, the highest among those of all the hydrocarbon polymers. © 1994 John Wiley & Sons, Inc.     

Synthesis and properties of a soluble and widely conjugated polyacetylene with anthryl pendant

The metathesis polymerization of an anthrylacetylene bearing an alkyl ester group, 9‐(10‐hexoxycarbonyl)anthrylacetylene ( 1 ), was conducted with various transition‐metal catalysts. A completely soluble black polymer was obtained from 1 in a good yield when W‐based catalysts were employed. The polymerization at a high monomer concentration (1 M) and a high temperature (80 °C) led to the formation of poly( 1 ) with a weight‐average molecular weight of 297 × 10³ in an 80% yield. The use of cocatalysts unexpectedly decreased both the yield and molecular weight of poly( 1 ). Rh‐catalyzed and Mo‐catalyzed polymerizations, however, resulted in poor yields of the polymer. The ultraviolet–visible spectrum of poly( 1 ) showed a significantly redshifted absorption (λ_max = 571) with a cutoff at 780 nm, which verified the very high order of conjugation of the main chain. Poly( 1 ) exhibited the largest third‐order nonlinear optical susceptibility [χ⁽³⁾ (−ω; ω, 0, 0) = − 1.9 × 10⁻¹⁰ esu] among the polymers from the monosubstituted polyacetylenes synthesized so far. The electrical conductivity of poly( 1 ) in an I₂‐doped state was 8.77 × 10⁻⁴ at 293 K. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4717–4723, 2000     

Electrochemical properties and photoelectrochemical response of vacuum-deposited poly(p-phenylene) thin films

The electrochemical properties of a poly(p-phenylene) (PPP) thin film prepared by vacuum deposition were investigated by cyclic voltammetry in organic and aqueous media with a lithium perchlorate electrolyte. The PPP thin film was able to undergo both n-doping and p-doping reversibly. In an aqueous medium, the cyclic voltammograms indicated the characteristic loop in a potential sweep. The loop was ascribed to the charge transfer on the PPP film surface and to an accumullation effect of the charge in the PPP film. A photocurrent was observed at the PPP film under UV light irradiation.     

亚砜还原法合成聚苯醚硫醚的结构与性能研究

以氟苯和氯化亚砜反应合成了4,4’-二氟二苯亚砜,并将其与4,4’二羟基二苯硫醚在N-甲基吡咯烷酮溶剂中进行亲核取代反应合成了聚苯醚硫醚醚亚砜,用乙二酰氯/四丁基碘化铵还原该亚砜聚合物制备了聚苯醚硫醚。用红外光谱和核磁共振谱对合成单体的结构进行了确认,同时对聚合物进行了红外光谱、核磁共振、元素分析、X射线光电子能谱、X射线衍射、DSC分析、TG/DTG以及溶解性测试。结果表明聚苯醚硫醚样品具有氧醚和硫醚交替的线性结构,特性粘度为0.55 dL/g的PPSE熔点达236℃,在氮气条件下,样品起始分解温度和最大分解速率处温度分别为359℃和514℃,在700℃时的重量保留率为43.3%,且在加热条件下能溶解于N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)等极性有机溶剂中。     

Synthesis and properties of poly(hydroxyurethane)s

Bis(cyclic Carbonate)s 1 were prepared by the reaction of bis(epoxide)s and atmospheric pressure of CO₂ in the presence of sodium iodide and triphenylphosphine as catalysts at 100°C in high yield. Polyaddition of 1 and hexamethylenediamine ( 2a ) or dodecamethylenediamine ( 2b ) in dimethylsulfoxide or N,N-dimethylacetamide (DMAc) at 70 or 100°C for 24 h afforded corresponding poly(hydroxyurethane)s with M?_n 20,000–30,000. When ethylenediamine ( 2c ) or 1,3-propanediamine ( 2d ) was used as a diamine, poly(hydroxyurethane)s with lower molecular weight were obtained. The presence of water, methanol, or ethyl acetate in the solvent had little effect on the M?_n of the polymer obtained, because of the high chemoselectivity of the reaction of the five-membered cyclic carbonate and amine. Polyaddition of bis(cyclic carbonate) bearing ester groups and 2a also afforded the corresponding poly(hydroxyurethane) without aminolysis of the ester groups. Poly(hydroxyurethane) 3 obtained from the bis(cyclic carbonate) derived from bisphenol A was less soluble in organic solvents than model polyurethane 8 having no hydroxy groups obtained from 4,4′-isopropylidenebis(2-hydroxyethoxybenzene) and hexamethylene diisocyanate, and was thermally stable as well as 8.3 easily undertook crosslinking at room temperature by the treatment with hexamethylene diisocyanate or aluminium triisopropoxide in DMAc or tetrahydrofuran. The gel crosslinked by aluminium triisopropoxide regenerated the original polymer at room temperature by treatment with 1.5 equiv of 1.2M HCl in N-methylpyrollidinone for 1 h. © 1993 John Wiley & Sons, Inc.