Miscibility of C60-end-capped poly(ethylene oxide) with poly(vinyl chloride)

The miscibility of blends of single [60]fullerene (C₆₀)-end-capped poly(ethylene oxide) (FPEO) or double C₆₀-end-capped poly(ethylene oxide) (FPEOF) with poly(vinyl chloride) (PVC) has been studied. Similar to poly(ethylene oxide) (PEO), both FPEO and FPEOF are also miscible with PVC over the entire composition range. X-ray photoelectron spectroscopy showed the development of a new low-binding-energy Cl2p doublet and a new high-binding-energy O1s peak in FPEO/PVC blends. The results show that the miscibility between FPEO and PVC arises from hydrogen bonding interaction between the α-hydrogen of PVC and the ether oxygen of FPEO. From the melting point depression of PEO, FPEO or FPEOF in the blends, the Flory-Huggins interaction parameters were found to be −0.169, −0.142, −0.093 for PVC/PEO, PVC/FPEO and PVC/FPEOF, respectively, demonstrating that all the three blend systems are miscible in the melt. However, the incorporation of C₆₀ slightly impairs the interaction between PEO and PVC.     

Preparation and characterization of thiocyanate-selective electrodes based on new complexes of copper(II) as neutral carriers

The complexes of hydroxycitronellal (o-aminobenzoic acid) copper(II) (Cu(II)-HXAB) and salicylaldehyde (o-aminobenzoic acid) copper(II) (Cu(II)-SHAB) were used as neutral carriers in PVC-based membrane ion-selective electrodes. The electrode based on Cu(II)-HXAB exhibited near-Nernstian potential response to thiocyanate (SCN⁻) in a linear range of 1.0 × 10^− 6 to 1.0 × 10^− 1 M with a detection limit of 8.5 × 10^− 7 M and a slope of − 57.3 mV/decade in 0.01 M phosphate buffer solution (pH 5.0). The electrode exhibited high selectivity to SCN⁻ over other tested anions with an anti-Hofmeister selectivity sequence. The selectivity behavior might be discussed in terms of UV-Vis spectrum and infrared spectrum. The transfer process of thiocyanate across the membrane interface was investigated by making use of the AC impedance technique. The electrode containing Cu(II)-HXAB could be applied to thiocyanate analysis in waste water with satisfactory results.     

Highly salicylate-selective membrane electrode based on a new thiomacrocyclic Schiff base complex of binuclear copper(II) as neutral carrier

New binuclear metallic complexes of thiomacrocyclic Schiff base, 3,9,13,19 -tetraphenyl-6,16-dithione-1,11-dithio-4,5,7,8,14,15,17,18-octaazacycloeicosa-3,8,13,18-tetraene binuclear metal(II) [M(II)₂-TDDOCT] (M = Cu, Co, Ni), were synthesized and their anion response characteristics were investigated. The performances of the electrodes are considerably influenced by the nature of the central metals. The Cu(II) complex-based electrode exhibited a good selectivity to salicylate anion with an anti-Hofmeister selectivity pattern: Sal⁻ > ClO₄⁻ > SCN⁻ > I⁻ > Benzoate > B_r⁻ > Acetate > F⁻ > SO₃²⁻ > NO₂⁻ > Cl⁻ > NO₃⁻ > SO₄²⁻ > H₂PO₄⁻. The electrode had an excellent linear response to Sal⁻ from 9.0 × 10^− 7 to 1.0 × 10^− 1 M with a slope of − 59.3 mV per decade,a detection limit of 5.0 × 10^− 7 M, and a fast response time within 15 s over the entire concentration series in phosphate buffer solutions of pH 5.0 at 25 °C. Spectroscopic techniques and the influence of lipophilic charged additives on the electrode behavior were used to investigate the response mechanism to Sal⁻. The electrode can be applied to the direct determination of salicylate in human urine and pharmaceutical samples and the results obtained are in accord with the results from a standard method.     

Polyhedral oligomeric silsesquioxane as a novel plasticizer for poly(vinyl chloride)

This study focuses on investigating the use of polyhedral oligomeric silsesquioxanes (POSS) to plasticize poly(vinyl chloride) (PVC). Conventional organic plasticizers for PVC, such as dioctyl phthalate (DOP), are somewhat volatile, leading to plasticizer loss and unwanted deterioration of the material properties over time. Previous experimental results indicate that methacryl-POSS, which is much less volatile due to its hybrid organic-inorganic structure, has the ability to plasticize PVC. Methacryl-POSS is miscible in the PVC only up to 15 wt%, thereby limiting its suitability as a plasticizer. However, through the use of ternary compositions it is possible to increase the proportion of methacryl-POSS in PVC substantially. The T_g of appropriately formulated ternary PVC/POSS/DOP compounds can be reduced to near room temperature, and these materials exhibit desirable ductile behavior. Binary (PVC/DOP) and ternary (PVC/POSS/DOP) compounds formulated to the same T_g values showed considerably different mechanical properties. Such findings reveal the possibility of using POSS to engineer the mechanical properties of plasticized PVC.     

硬聚氯乙烯低发泡挤出成型研究

采用自由发泡挤出的方法研究了硬聚氯乙烯低发泡挤出成型的配方设计和工艺条件控制。讨论了稳定剂品种，改性剂品种和发泡剂用量对制品密度，泡孔结构以及外观表面的影响。还揭示了口模温度和螺杆转速与制品密度的关系。     

Preparation of a super-hydrophobic poly(vinyl chloride) surface via solvent-nonsolvent coating

A new simple approach was developed to obtain a super-hydrophobic PVC surface via solvent-nonsolvent coating without addition of low-surface-energy compounds. Also, the PVC film is nearly or still maintains its super-hydrophobicity when contacting with acid, alkali or salt solutions. SEM shows that compared with common smooth PVC surface, a lotus-like structure with micro- and nano-papillae was obviously observed on the hydrophobic PVC surfaces. Such a special surface microstructure may result in the super-hydrophobicity. A brief explanation to the formation of the special microstructure was put forward on the basis of diffusion, tension break and micro- and nano-phase separation.     

Application of Poly(butylenes 2-methylsuccinate) as Migration Resistant Plasticizer for Poly(vinyl chloride)

The bio-based and biodegradable polyester poly(butylenes 2-methylsuccinate) (PBM) was successfully used as a polymeric plasticizer to modify poly(vinyl chloride) (PVC) in this work. The tensile properties, plasticization efficiency estimated by the lowered glass transition temperature and the enhanced elongation at break of the PVC/PBM blends and the migration stability of the PBM were investigated. It was indicated that the migration-resistant property of PVC plasticized with PBM was greatly superior to that with dioctyl phthalate (DOP). Furthermore, the tensile properties were comparable to that of PVC/DOP, indicating that the environmentally friendly PBM can be used as an alternative plasticizer to remove the potential health risks from migrating phthalates during applications.     

Highly thiocyanate-selective membrane electrodes based on the N,N′-bis-(benzaldehyde)-glycine copper(II) complex as a neutral carrier

Some novel PVC membrane electrodes based on N,N′-bis-(benzaldehyde)-glycine metallic complexes of Cu(II), Ni(II), Zn(II) and Co(II) as neutral carriers are described. The results showed that the electrode based on the N,N′-bis-(benzaldehyde)-glycine copper(II) complex [Cu(II)-BBAG] had a near-Nernstian response to the thiocyanate ion ranging from 1.0×10⁻¹ to 9.0×10⁻⁷ M in a phosphate buffer solution of pH 4.0 with a detection limit of 7.0×10⁻⁷ M and a slope of −57.6 mV/decade at 25°C. The electrode displays an anti-Hofmeister selectivity sequence in the following order: SCN⁻>ClO⁻₄>Sal⁻>I⁻>Br⁻>NO⁻₂>NO⁻₃>SO²⁻₃>SO²⁻₄>Cl⁻>H₂PO The response mechanism is discussed in view of both AC impedance and UV spectroscopy techniques. The [Cu(II)-BBAG]-based electrode was successfully applied to the determination of the thiocyanate ion in wastewater and human saliva.     

Reactions of bis(3-aminopropyl)amine with formaldehyde in the presence of a metal ion: Preparation of a metal-free macropolycycle and a dinuclear copper(II) complex

The reaction of bis(3-aminopropyl)amine with excess formaldehyde in the presence of Ni²⁺ ion produces the macropentacyclic compound L¹(ClO₄)₂ (1) L¹ = 1,3,7,11,13,17- hexaazapentacyclo[15.3.1.1^3.7.1^7.13.1^13.17]tetracosane). The dinuclear complex [Cu₂(L²)₂(H₂O)₂](ClO₄)₂ (2) (HL¹ = 1-(3-aminopropyl)-3-(hydroxymethyl)-1,3-diazacyclohexane) as well as 1 can be prepared by the condensation reaction in the presence of Cu²⁺ ion. Interestingly, 2 · 2H₂O exhibits uncommon magnetic behavior.     

Novel micelle-forming block copolymer composed of poly (ε-caprolactone) and poly(vinyl pyrrolidone)

The well-defined poly (ε-caprolactone) (PCL)/poly(vinyl pyrrolidone) (PVP) diblock copolymers were synthesized through combining radical polymerization of VP and the controlled coordination-insertion ring-opening polymerization of CL using an aluminum alkoxide macroinitiator formed from the equimolar reaction of triethylaluminum with hydroxy-terminated PVP (PVP-OH). The molecular characterization of PCL/PVP diblock copolymers was confirmed through ¹H NMR spectroscopy and GPC analysis. Polymeric micelles composed of PCL as a hydrophobic core and PVP as a hydrophilic shell were prepared by a diafiltration method. The micellar properties such as sizes, shapes, and critical micelle concentrations (CMC) were investigated with a dynamic light scattering (DLS) spectrometer, transmission electron microscope (TEM) and spectrofluorimeter. The sizes of micelles ranged from 30 to 80 nm in average size. The novel micelles formed from the well-defined PCL/PVP diblock copolymers seem to be feasible as novel promising carriers in biomedical and pharmaceutical applications.     

Biosorption of copper (II) from aqueous solutions by wheat shell

The adsorption capacity of wheat shell for copper (II) was studied at various pH (2-7), agitation speeds (50-250 rpm) and initial metal ion concentrations (Co, from 10 to 250 mg.L⁻¹). Maximum biosorption of copper onto wheat shell occurred at 240 rpm agitation speed and at pH between 5 and 6. The biosorption values of copper (11) were increased with increasing pH from 2 to 5 and decreased with increasing copper/wheat shell (x/m) ratios from 0.83 to 10.84 mgCu(II).g⁻¹ wheat shell. The biosorption efficiencies at these x/m ratios were 99% and 52%, respectively, at the end of the 120 min contact time (t). The equilibrium isotherms and kinetics were obtained from batch adsorption experiments at 298 K. It was observed that wheat shell was a suitable biosorbent for removing Cu(II) from aqueous solutions.     

弹性体改性软质聚氯乙烯性能的研究

讨论了不同品种的弹性体对软质氯乙烯的改性结果,包括不同品种和不同含量的弹性体对ＰＶＣ力学性能等性能的影响,实验了得到了性能较好的改性ＰＶＣ软质材料。     

给水管用PVC的改性研究

采用活性碳酸钙和甲基丙烯酸甲酯-丁二烯-苯乙烯三元接枝共聚物(MBS)对PVC进行改性,研究了二者对改性PVC抗冲击性能的影响.结果表明,活性碳酸钙和MBS的加入,改性PVC的抗冲击性能可提高17.3％,改性PVC管在低温下的抗冲击性能得到明显提高.     

Modification of poly(vinyl chloride) films by aliphatic amines to prepare anion-exchange membranes for Cr (VI) removal

ABSTRACT

A method for the synthesis of anion-exchange membranes by the grafting of ethylenediamine (EDA), diethylenetriamine (DETA) or pentaethylenehexamine (PEHA) onto poly(vinyl chloride) (PVC) film has been presented. The chemical structure was determined by means of Fourier Transform Infrared Spectroscopy (FTIR) and the membranes were characterized by ion-exchange capacity, chloride and nitrogen contents, water regain and surface energetics. The obtained membranes were evaluated in the Donnan dialysis (DD) of hexavalent chromium solutions. Among the membranes, those modified with EDA and DETA showed the best separation features: high flux and high recovery factor (RF). The highest degree of recovery was observed for membranes prepared by the casting of PVC solution in (THF), followed by grafting EDA.     

Kinetics of ligand exchange reaction of Cu(II)-ammine complex with poly(vinyl alcohol) in aqueous solution

The kinetics of the ligand exchange reaction of the Cu(II)-ammine complex with poly(vinyl alcohol) (PVA) has been studied by a stopped-flow method at pH 9–10, at μ=0.1 (NH₄Cl) and at 25°C. The reaction is initiated by the formation of unstable [Cu(NH₃)₃]²⁺ by the attack of H⁺ on Cu(II)-ammine complex, and proceeds through the mixed complex {[Cu(NH₃)₃(O?PVA)]²⁺}. This step may be rate-determining, followed by a rapid reaction. Finally, the Cu(II) ion is taken up by PVA. The rate is given by d[Cu(II)?PVA]/dt=k[H⁺]{[Cu(NH₃)₄]²⁺}[PVA]/[NH₄Cl], where k=k₁ + k′₂[H⁺], k₁=4.25× 10s^?1 and k′₂=5.20× 10¹¹l mol^?1s^?1.     

Hydrophilic surface modification of poly(vinyl chloride) film and tubing using physisorbed free radical grafting technique

The grafting of hydrophilic monomers from the surface of PVC films and complex geometries, such as tubing, was executed by a novel two-step process: physisorption of a hydrophobic free radical initiator onto a polymer surface followed by radical polymerization with hydrophilic monomers. The key step is creating a hydrophobic/hydrophilic diffusional barrier that promotes radical generation upon heating at the polymer surface. Transmission infrared spectroscopy, X-ray photoelectron spectroscopy, surface wettability and capillary rise, gravimetric analysis, UV-vis spectroscopy and gel permeation chromatography were utilized to prove successful covalent grafting of poly(hydroxyethylmethacrylate), poly(dimethylacrylamide), poly(hydroxyethylacrylate), poly(dimethylaminoethylmethacrylate), poly(acrylic acid), and poly(4-vinyl pyridine).     

Study on the Thermal Stability and Stabilization Mechanism of a Novel Thermal Stabilizer for Rigid Poly (Vinyl Chloride)

A novel thermal stabilizer for rigid poly (vinyl chloride) has been examined. Its high stabilizing efficiency is detected by the extent of discoloration and the mass loss rate of the degraded samples when compared with some of reference stabilizers. A higher stabilizing efficiency is produced as the novel thermal stabilizer is mixed with different co-stabilizers. The study results for thermo oxidative stability of the degraded samples with novel thermal stabilizer have shown that the novel thermal stabilizer can prevent or delay the thermal oxidative degradation of PVC. A probable stabilization mechanism for the novel thermal stabilizer has been proposed.     

Gradient doping of Cu(I) and Cu(II) in ZnO nanorod photoanode by electrochemical deposition for enhanced photocurrent generation

This study describes the synthesis and characterization of Cu-doped ZnO nanorods (NRs) by an electrochemical method in the presence of two different Cu precursor (Cu⁺² and Cu⁺) in order to improve photocurrent generation. Analyses of the resulting materials by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–Vis and electrochemical photocurrent (ECP) spectroscopy confirm the formation of well-aligned ZnO Würtzite nanostructures in the form of hexagonal rods. For both doping source with a concentration of up to 0.5%, the following changes were observed: a distortion of the ZnO morphology, an increase in transmittance to 96% for ZnO doped with Cu⁺², and a reduction of the energy gap from 3.36 eV to 3.06 and 3.02 eV for ZnO doped with Cu⁺² and Cu⁺, respectively. From photoelectrochemical tests, the photo-current density was improved up to 0.05 mA cm^-2 in the presence of Cu doping, which is twelve times superior to that of undoped ZnO nanorods, which means that the incorporation of Cu+2 or Cu + significantly improves the separation efficiency of photogenerated electron-hole pairs. These results can be considered promising for optoelectronic and photocatalysis applications.     

Preparation and characterization of composite resin by vinyl chloride grafted onto poly(BA-EHA)/poly(MMA-St)

Crosslinked poly(butyl acrylate-co-2-ethylhexyl acrylate)/poly(methyl methacrylate-co-styrene) (ACR I) latex was synthesized by multi-stage emulsion polymerization. A series of grafting vinyl chloride (VC) composite latices were prepared by emulsion copolymerization in the presence of core-shell ACR I latex. The effects of ACR I amount and its core/shell ratio on particle diameters of the composite latices and mechanical properties of the prepared materials were investigated. The grafting efficiency (GE) of VC grafted onto ACR I increases with an increasing ACR I content. Transmission electron microscope (TEM) study indicates that ACR I latex particles have a regular core-shell structure obviously. However, when styrene content in the shell of ACR I is more than 70 percent of the shell by weight, ACR I latex particles have an irregular core-shell morphology like sandwich. The composite latex particles synthesized by core-shell ACR I latex grafting VC have a clear three-layered core-shell structure. Dynamic mechanical analysis (DMA) study reveals that the compatibility between ACR I and PVC is well improved. With increasing ACR I content, the loss peak in low temperature range for every composite sample becomes stronger and stronger and gradually shifts to a higher temperature. Scanning electron microscope (SEM) graphs showed that the fractured surface of the composite sample exhibited better toughness of the material. TEM graphs showed that ACR I was uniformly dispersed in the PVC matrix.