EFFECTS OF MOLECULE AGGREGATION STATE OF HINDERED PHENOL ON DYNAMIC MECHANICAL PROPERTIES OF CHLORINATED POLYETHYLENE*

Hindered phenol compound 3,9-bis{1,1-dimethyl-2[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro[5,5]-undecane (AO-80) is a polymorphous material with different physical structures. The initial AO80 is highly crystalline, whereas AO-80 obtained by cooling from its molten state is an amorphous material. Annealing treatment below the melting point of AO-80 results in structural development. The mixture of chlorinated polyethylene (CPE) and vitrified AO-80 particles exhibits a dramatic change in the dynamic mechanical properties during heat treatment at 130℃. This change can be attributed to the decomposition of the vitrified AO-80 particles and the hybridization of two constituents. The vitrified AO-80 particles can crystallize again in a CPE matrix by annealing at 100℃, but this crystal is different from that of the initial AO-80 in its microstructure. In addition, the incorporation of CPE chains caused a dramatic increase in the modulus. As a result, the AO-80 crystal particles that contain some CPE chains act as multifunctional crosslinks and the CPE/AO-80 hybrid was found to be a new type of elastomer.     

Organic hybrid of chlorinated polyethylene and hindered phenol. I. Dynamic mechanical properties

Dynamic mechanical properties and microstructure of an organic hybrid consisting of chlorinated polyethylene (CPE) and 3,9‐bis[1,1‐dimethyl‐2{β‐(3‐tert‐butyl4‐hydroxy‐5‐methylphenyl)propionyloxy}ethyl]‐2,4,8,10‐tetraoxaspiro[5,5]‐undecane (AO‐80) were investigated. The AO‐80 clearly exhibited two second‐order transitions at 6 and 69 °C in addition to the melting: the transition at lower temperature is assigned to the glass transition, and the transition at higher temperature is considered to be caused by the dissociation of hydrogen bond between the hydroxyl groups of AO‐80. When blending with CPE, part of AO‐80 molecules was dispersed into the CPE matrix, and most of them formed an AO‐80‐rich phase. As a result, a novel transition appeared above the glass‐transition temperature of the CPE matrix. It was assigned to the dissociation of the intermolecular hydrogen bond between the α‐hydrogen of CPE and the hydroxyl groups of AO‐80 within the AO‐80‐rich phase. Dynamic mechanical properties and microstructure of CPE/AO‐80 hybrid were controlled by the thermal treatment. It was found that the CPE/AO‐80 hybrid is a good damping material and shows a shape memory effect. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2285–2295, 2000     

Organic hybrid of chlorinated polyethylene and hindered phenol. III. Influence of the molecular weight and chlorine content of the polymer on the viscoelastic properties

The influences of the molecular weight and chlorine content of chlorinated polyethylene (CPE) on the dynamic mechanical propertiesof an organic hybrid consisting of CPE and 3,9‐bis[1,1‐dimethyl‐2{β‐(3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl)propionyloxy}ethyl]‐2,4,8,10‐tetraoxaspiro[5,5]‐undecane (AO‐80) were investigated. All CPE/AO‐80 hybrids clearly exhibited two kinds of relaxations, and their magnitudes varied according to the molecular weight and chlorine content of CPE. This was due to a change in the ratio of AO‐80 molecules dispersed in the CPE‐rich domain and the AO‐80‐rich domain. A comparison of the jump intensity in differential scanning calorimetry curves with the maximum value of the second tan δ peak demonstrated that the second relaxation was caused by the dissociation of intermolecular hydrogen bonding within the AO‐80‐rich domain. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2943–2953, 2000     

Organic hybrid of chlorinated polyethylene and hindered phenol. IV. Modification on dynamic mechanical properties by chlorinated paraffin

Binary systems of chlorinated polyethylene (CPE) and chlorinated paraffin (CP) or 3,9‐bis[1,1‐dimethyl‐2{β‐(3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl) propionyloxy}ethyl]‐2,4,8,10‐tetraoxaspiro[5,5]‐undecane (AO‐80) and their ternary systems were investigated by dynamic mechanical analysis, thermal analysis, and infrared spectrum analysis. Adding CP into CPE/AO‐80, in which one novel relaxation appears above the glass‐transition temperature of CPE, can increase not only the peak height but also the minimum value between two peaks. The tan δ value in the middle of the two peaks for CPE/CP/CPE was found to be proportional to the slope (d ln E′/dT) of the E′ curve at an identical temperature. The addition of CP caused changes in many of the hydrogen bonds: a decrease in hydrogen bonds between the hydroxyl groups of AO‐80, a reinforcement of hydrogen bonds between the hydroxyl groups of AO‐80 and α‐hydrogens of CPE, and the formation of other hydrogen bonds between the carbonyl groups of AO‐80 and α‐hydrogens of CPE. Those changes are useful to improve the temperature dependence of tan δ and to enhance the stability of the dynamic mechanical properties. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 23–31, 2001     

Organic hybrid of chlorinated polyethylene and hindered phenol. II. Influence of the chemical structure of small molecules on viscoelastic properties

The viscoelastic properties and stabilities of those properties of organic hybrids consisting of chlorinated polyethylene (CPE) and tetrakis[methylene‐3‐(3‐5‐di‐tert‐butyl‐4‐hydroxy phenyl)propionyloxy]methane (AO‐60) and triethylene glycol bis[3‐(3‐tert‐butyl‐4‐hydroxy‐5‐methyl phenyl)propionyloxy] (AO‐70) were investigated. The CPE/AO‐70 hybrids show only one transition, whereas for the CPE/AO‐60 hybrids, one novel relaxation appears above the glass‐transition temperature of CPE. This relaxation on the higher temperature side in the mechanical spectrum for CPE/AO‐60 is associated with the appearance of the AO‐60‐rich phase. Furthermore, the stabilities of the viscoelastic properties and microstructures of the organic hybrids consisting of CPE and multifunctional hindered phenols are dominated by the strength of the intermolecular interaction between CPE and phenols and the conformations of the middle skeletal parts of hindered phenols. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1496–1503, 2000     

Microthermal analysis of the melting behavior in zone‐drawn isotactic polypropylene fibers

A microthermal analysis (μTA) method with an ultrahigh heating rate was applied to a zone‐drawn isotactic polypropylene fiber to evaluate the melting behaviors inherent to the microstructural changes occurring during the drawing process. The μTA melting point decreased with a reduction in the melting temperature because of the suppression of crystal reorganization and increased with an increase in the melting temperature because of the suppression of the relief of the orientation of the molecular chains, in comparison with the conventional melting point obtained by traditional differential scanning calorimetry. This study examined a convenient and powerful method for investigating the melting behavior for polymeric materials inherent to the original microstructure with less influence from thermal‐measurement heating. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3677–3681, 2004     

Synthesis of water‐dispersible,fluorinated particles with grafting sulfonate chains by the core crosslinking of block copolymer micelles

Fluorinated polymer particles with grafting sulfonate chains, which showed high dispersion stability in aqueous media, were synthesized by the crosslinking of block copolymer micelles. A crosslinkable block copolymer, poly[(2,3,4,5,6‐pentafluorostyrene)‐co‐4‐(1‐methylsilacyclobutyl)styrene]‐b‐poly(neopentyl 4‐styrenesulfonate), composed of a statistical copolymer segment of 2,3,4,5,6‐pentafluorostyrene with 4‐(1‐methylsilacyclobutyl)styrene and a neopentyl 4‐styrenesulfonate segment, was prepared by the nitroxy‐mediated living radical polymerization of a 2,3,4,5,6‐pentafluorostyrene/4‐(1‐methylsilacyclobutyl)styrene mixture and neopentyl 4‐styrenesulfonate. The block copolymer formed micelles with a poly[(2,3,4,5,6‐pentafluorostyrene)‐co‐4‐(1‐methylsilacyclobutyl)styrene] core in acetonitrile, which were crosslinked via the ring‐opening reaction of silacyclobutyl groups in the core by a treatment with a platinum catalyst. The deprotection of sulfonate groups in the micelle corona by exposure to trimethylsilyl iodide and a treatment with aqueous HCl, followed by neutralization with aqueous NaOH, provided a polymer particle with polymer chains of sodium 4‐styrenesulfonate grafted on its surface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1316–1323, 2007     

Crystallization of poly(ethylene terephthalate–co–isophthalate)

Melt crystallization behaviors of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐isophthalate) (PETI) containing 2 and 12 mol % of noncrystallizable isophthalate components were investigated. Differential scanning calorimetry (DSC) isothermal results revealed that the introduction of 2 mol % isophthalate into PET caused a change of the crystal growth process from a two‐dimensional to a three‐dimensional spherulitic growth. The addition of more isophthalate up to 12 mol % into the PET structure induced a change in the crystal growth from a three‐dimensional to a two‐dimensional crystal growth. DSC heating scans after completion of isothermal crystallization at various T_c's showed three melting endotherms for PET and four melting endotherms for PETI‐2 and PETI‐12. The presence of an additional melting endotherm is attributed to the melting of copolyester crystallite composed of ethylene glycol, tere‐phthalate, and isophthalate (IPA) or the melting of molecular chains near IPA formed by melting the secondary crystallite T_m (I) and then recrystallizing during heating. Analyses of both Avrami and Lauritzen‐Hoffman equations revealed that PETI containing 2 mol % of isophthalate had the highest Avrami exponent n, growth rate constant G_o, and product of lateral and end surface free energies σσ_e. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2515–2524, 2000     

Oriented crystallization of poly(L‐lactic acid) in uniaxially oriented blends with poly(vinylidene fluoride)

This article describes the oriented crystallization of poly(L ‐lactic acid) (PLLA) in uniaxially oriented blends with poly(vinylidene fluoride) (PVDF). Uniaxially drawn films of PLLA/PVDF blend with fixed ends were heat‐treated in two ways to crystallize PLLA in oriented blend films. The crystal orientation of PLLA depended upon the heat‐treatment process. The crystal c‐axis of the α form crystal of PLLA was highly oriented in the drawing direction in a sample cold‐crystallized at T_c = 120 °C, whereas the tilt‐orientation of the [200]/ [110] axes of PLLA was induced in the sample crystallized at T_c = 120 °C after preheating at T_p = 164.5–168.5 °C. Detailed analysis of the wide‐angle X‐ray diffraction (WAXD) indicated that the [020]/ [310] crystal axes were oriented parallel to the drawing direction, which causes the tilt‐orientation of the [200]/ [110] axes and other crystal axes. Scanning electron microscopy (SEM) suggested that oriented crystallization occurs in the stretched domains of PLLA with diameters of 0.5–2.0 μm in the uniaxially drawn films of PVDF/PLLA = 90/10 blend. Although the mechanism for the oriented crystallization of PLLA was not clear, a possibility was heteroepitaxy of the [200]/[110] axes of the α form crystal of PLLA along the [201]/[111] axes of the β form crystal of PVDF that is induced by lattice matching of d₁₀₀(PLLA) ≈ 5d₂₀₁(PVDF). © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1376–1389, 2008     

PMMA colloid particles armored by clay layers with PDMAEMA polymer brushes

Poly[2‐(dimethylamino) ethyl methacrylate] (PDMAEMA) brushes on the surfaces of clay layers were prepared by in situ free‐radical polymerization. Poly (methyl methacrylate) (PMMA) colloid particles stabilized and initiated by clay layers with PDMAEMA polymer brushes were prepared by Pickering emulsion polymerization. Transmission electron microscopy was used to characterize the structure and morphology of the colloid particles. The X‐ray diffraction (XRD) results indicated that the intercalated structures of the clay layers were almost destroyed in Pickering emulsion polymerization, and clay layers with exfoliated structures were created. The surface of the colloid particles was analyzed by using X‐ray photoelectron spectroscopy (XPS). The XPS results provide direct evidence that the clay layers with PDMAEMA chains cover the PMMA colloid particles. © 2008 Wiley Periodicals, Inc. JPolym Sci Part A: Polym Chem 46: 2632–2639, 2008     

Synthesis of double hydrophilic graft copolymer containing poly(ethylene glycol) and poly(methacrylic acid) side chains via successive ATRP

A well‐defined double hydrophilic graft copolymer, with polyacrylate as backbone, hydrophilic poly(ethylene glycol) and poly(methacrylic acid) as side chains, was synthesized via successive atom transfer radical polymerization followed by the selective hydrolysis of poly(methoxymethyl methacrylate) side chains. The grafting‐through strategy was first used to prepare poly[poly(ethylene glycol) methyl ether acrylate] comb copolymer. The obtained comb copolymer was transformed into macroinitiator by reacting with lithium diisopropylamine and 2‐bromopropionyl chloride. Afterwards, grafting‐from route was employed for the synthesis of poly[poly(ethylene glycol) methyl ether acrylate]‐g‐poly(methoxymethyl methacrylate) amphiphilic graft copolymer. The molecular weight distribution of this amphiphilic graft copolymer was narrow. Poly(methoxymethyl methacrylate) side chains were connected to polyacrylate backbone through stable C? C bonds instead of ester connections. The final product, poly[poly(ethylene glycol) methyl ether acrylate]‐g‐poly(methacrylate acid), was obtained by selective hydrolysis of poly(methoxymethyl methacrylate) side chains under mild conditions without affecting the polyacrylate backbone. This double hydrophilic graft copolymer was found be stimuli‐responsive to pH and ionic strength. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4056–4069, 2008     

Emulsion synthesis of nanoparticles containing PEDOT using conducting polymeric surfactant: Synergy for colloid stability and intercalation doping

Poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) is a widely used conductive aqueous dispersion synthesized by using emulsion polymerization method. To further enhance its solution processability and conductivity of PEDOT derivatives, we proposed to replace the nonconductive PSS with conductive poly[2‐(3thienyl)‐ethoxy‐4‐butylsulfonate] (PTEB) as surfactant for the emulsion polymerization of PEDOT. The reaction involved colloid stabilization and doping in one step, and yielded PEDOT:PTEB composite nanoparticles with high electrical conductivity. Contrary to its counterpart containing nonconductive surfactant, PEDOT: PTEB showed increasing film conductivity with increasing PTEB concentration. The result demonstrates the formation of efficient electrical conduction network formed by the fully conductive latex nanoparticles. The addition of PTEB for EDOT polymerization significantly reduced the size of composite particles, formed stable spherical particles, enhanced thermal stability, crystallinity, and conductivity of PEDOT:PTEB composite. Evidence from UV–VIS and FTIR measurement showed that strong molecular interaction between PTEB and PEDOT resulted in the doping of PEDOT chains. X‐ray analysis further demonstrated that PTEB chains were intercalated in the layered crystal structure of PEDOT. The emulsion polymerization of EDOT using conducting surfactant, PTEB demonstrated the synergistic effect of PTEB on colloid stability and intercalation doping of PEDOT during polymerization resulting in significant conductivity improvement of PEDOT composite nanoparticles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2536–2548, 2008     

Copolymerization of ethylene with cycloolefins or cyclodiolefins by a constrained‐geometry catalyst

The copolymerization of ethylene and cycloolefins [cyclopentene (CPE), cyclohexene (CHX), cycloheptene (CHP), cyclooctene (COT), cyclododecene (CDO), norbornene (NB), and 5,6‐dihydrodicyclopentadiene HDCPD] and cyclodiolefins [1,3‐cyclopentadiene (CPD), 1,4‐cyclohexadiene (CHD), 1,5‐cyclooctadiene (COD), 2,5‐norbornadiene (NBD), and dicyclopentadiene (DCPD)] was investigated with a constrained‐geometry catalyst, dimethylsilylene(tetramethylcyclopentadienyl)(N‐tert‐butyl)titanium dichloride, with methyl isobutyl aluminoxane as a cocatalyst. In the copolymerization with cycloolefins, the olefins, except for CHX, CDO, and HDCPD, were copolymerized via the 1,2‐insertion mode with the following reactivity: NB > CHP > COT > CPE. In the copolymerization with cyclodiolefins, corresponding copolymers, except for copolymerization with CHD, were obtained. A crosslinking fraction was detected in the copolymers with COD and NBD. The reactivity of the cyclodiolefins, except for COD, was higher than that of the cycloolefins. CPD was copolymerized via 1,2‐insertion, 1,4‐insertion or 1,2‐insertion of dimerized DCPD. The copolymerization with COD showed peculiar behavior under the copolymerization condition of a high COD concentration in the feed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1285–1291, 2005     

pH‐responsive polyphosphonates using butler's cyclopolymerization

The cationic monomer, N,N‐diallyl‐(diethylphosphonato)methylammonium chloride, and zwitterionic monomer, ethyl 3‐(N,N‐diallylammonio)methanephosphonate, were cyclopolymerized in aqueous solutions using ammonium persulfate or t‐butylhydroperoxide as initiators to afford a cationic polyelectrolyte (CPE) and a polyzwitterion ester (PZE), respectively. The CPE and PZE on acidic hydrolysis of the ester functionalities afforded the same polyzwitterionic acid (PZA): poly[3‐(N,N‐diallylammonio)methanephosphonic acid]. The solution properties of the CPE, pH‐responsive PZE, and PZA were studied in detail by potentiometric and viscometric techniques. Basicity constants of the phosphonate (P?O(OEt)O^?) and amine groups in the PZE and in the conjugate base of the PZE, respectively, were found to be “apparent” and as such follow the modified Henderson–Hasselbalch equation. In contrast to many polycarbobetaines and sulfobetaines, PZE was found to be soluble in salt‐free water as well as salt (including Ca²⁺, Li⁺)‐added solutions, and demonstrated “antipolyelectrolyte” solution behavior. The PZA, on the other hand, was found to be insoluble in salt‐free water, and on treatment with NaOH gave dianionic polyelectrolyte (DAPE) containing trivalent nitrogen and [P?O(O)₂^2?] groups. For the first time, several new phase diagrams of polyethylene glycol‐DAPE aqueous two‐phase systems (ATPSs) have been constructed in the presence of varying proportions of HCl. The ATPSs may find application in affinity partitioning of metal ions because DAPE is expected to be an effective chelator. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Uni‐molecular nanoparticles of poly(2‐oxazoline) showing tunable thermoresponsive behaviors

Herein, cylindrical molecular bottlebrushes grafted with poly(2‐oxazoline) (POx) as a shaped tunable uni‐molecular nanoparticle were synthesized via the grafting‐onto approach. First, poly(glycidyl methacrylate) (PGMA) backbones with azide pendant units were prepared via reversible addition fragmentation transfer (RAFT) polymerization followed by post‐modification. The degree of polymerization (DP) of the backbones was tuned in a range from 20 to 800. Alkynyl‐terminated POx side chains were synthesized by living cationic ring opening polymerization (LCROP) of 2‐ethyl‐2‐oxazoline (EtOx) and 2‐methyl‐2‐oxazoline (MeOx), respectively. The DP of side chains was varied between 20 and 100. Then, the copper‐catalyzed azide‐alkynyl cycloaddition (CuAAC) click chemistry was conducted with a feed ratio of [alkynyl]:[azide] = 1.2:1 to yield a series of brushes. Depending on the DP of side chains, the grafting density ranged between 47 and 85%. The resulting brushlike nanoparticles exhibited shapes of sphere, rod and worm. Aqueous solutions of PEtOx brushes demonstrated a thermoresponsive behavior as a function of the length of backbones and side chains. Surprisingly, it was found that the lower critical solution temperature of PEtOx brushes increased with a length increase of backbones. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 174–183     

Poly(thiodiethylene adipate): Melting behavior,crystallization kinetics,morphology, and crystal structure

The melting behavior and crystallization kinetics of poly(thiodiethylene adipate) (PSDEA) were investigated with differential scanning calorimetry and hot‐stage optical microscopy. The observed multiple endotherms, commonly displayed by polyesters, were influenced by the crystallization temperature (T_c) and ascribed to melting and recrystallization processes. Linear and nonlinear treatments were applied to estimate the equilibrium melting temperature for PSDEA with the corrected values of the melting temperature. The nonlinear estimation yielded a higher value by about 9 °C. Isothermal crystallization kinetics were analyzed according to Avrami's treatment. Values of Avrami's exponent close to 3 were obtained, independently of T_c, in agreement with a crystallization process originating from predetermined nuclei and characterized by three‐dimensional spherulitic growth. As a matter of fact, space‐filling spherulites were observed by optical microscopy at all T_c's. The rate of crystallization became lower as T_c increased, as usual at a low undercooling, the crystallization process being controlled by nucleation. Moreover, the crystal structure of PSDEA was determined from powder X‐ray diffraction data by full profile fitting. A triclinic unit cell containing two polymer chains arranged parallel to the c axis was found. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 553–566, 2004     

Effect of stereosequences on crystallinity and properties of zone‐drawn poly(vinyl alcohol) microfibrils

To effectively orient the molecular chains of novel syndiotactic poly(vinyl alcohol) (PVA) microfibrillar fiber (PVA fibril), a high‐temperature zone‐drawing method was adopted. The PVA fibrils were directly prepared from the saponification and in situ fibrillation without a spinning procedure. The maximum draw ratio of the PVA fibril increased with a decrease in the syndiotactic diad (r‐diad) content, indicating that the deformability of PVA molecules was lowered in higher syndiotactic PVA. Degree of crystal orientations up to 0.990 were achieved by stretching the PVA fibril with the r‐diad content of 65.1% and the original degree of crystal orientation of 0.902 at 250 °C close to its crystal melting temperature (T_m). When the same draw ratio was applied to the fibrils, a higher crystal orientation was achieved for the fibrils having higher syndiotacticity. Wide‐angle X‐ray data show that the longitudinal crystal sizes of drawn PVA fibrils were larger in higher syndiotacticities. The degree of crystal orientation, crystallinity, T_m, longitudinal crystal size, and tensile strength of the maximum drawn PVA fibril with a r‐diad content of 65.1% were 0.99, 0.97, 279 °C, 187 Å, and 4.66 N/tex, respectively. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1263–1271, 2001     

Molecular orientation and composition at the surface of spin‐coated polyfluorene:Fullerene blend films

The surface composition in spin‐coated films of polyfluorene:fullerene blends was determined quantitatively by near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy. By comparing partial and total electron yield spectra, we found vertical compositional differences in the surface region. Furthermore, the orientation of the polymer chains was investigated by variable‐angle NEXAFS. Blend films of poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐co‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole] with [6,6]‐phenyl‐C61‐butyric acid methyl ester in two different blend ratios were studied. Results showed polymer enrichment of the surfaces for films with a polymer:fullerene weight ratio of 20:80 and of 50:50, spin‐coated from both chlorobenzene and chloroform solutions. The angular dependence of the NEXAFS spectra of the pure polymer films showed a preferential plane‐on orientation, which was slightly stronger in the subsurface region than at the surface. In blend films, this orientational preference was less pronounced and the difference between surface and subsurface vanished. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Synthesis and characterization of new copolyacrylates containing porphyrin units as pendant groups and their use as sensors

Novel copolyacrylates containing various molar ratios of 5,10,15‐tri[p‐(9‐methoxy‐triethylenoxy)phenyl]‐20‐(p‐acryloxyphenyl)porphyrin units in the chains have been synthesized, and their chemical structure was determined by NMR and MALDI‐TOF mass spectrometry. Sensing response of the synthesized copolymers has been tested for trifluoroacetic and hydrochloric acids and nitrogen dioxide analytes. The reported sensing data indicate that porphyrin units are interacting with analytes in a reversible fashion. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Two Keggin Templated Supramolecular Compounds by Exerting the Chelate and Linking Dual Roles of the Ligand 2, 2′‐Biimidazole

Two new Keggin templated supramolecular compounds, [Zn₂(H₂biim)₅(SiM₁₂O₄₀)] · 4H₂O [M = W ( 1 ), Mo ( 2 )] (H₂biim = 2, 2′‐biimidazole), were synthesized under hydrothermal conditions by using the ligand 2, 2′‐biimidazole. They were characterized by single‐crystal X‐ray diffraction, elemental analyses, IR and photoluminescence spectroscopy as well as cyclic voltammetry. The two isostructural compounds are constructed by two discrete supramolecular moieties: the inorganic chains consist of Keggin anions and metal‐organic chains constructed by [Zn₂(H₂biim)₅]⁴⁺ subunits. In the dinuclear [Zn₂(H₂biim)₅]⁴⁺ subunit, the H₂biim ligands exhibit a dual role, chelating and linking. The metal‐organic chains further construct a 3D supramolecular framework with channels, in which the Keggin‐based inorganic chains are accommodated. The electrochemical behaviors of compounds 1 and 2 bulk‐modified carbon paste electrodes ( 1 ‐CPE, 2 ‐CPE) were studied.