Graft copolymers of poly(methyl methacrylate) and polyamide-6 via in situ anionic polymerization of ε-caprolactam and their properties

Graft copolymers of poly(methyl methacrylate) and polyamide-6 (PMMA-g–PA6) were investigated via in situ anionic polymerization of ε-caprolactam, using PMMA precursors with N-carbamated caprolactam pendants (PMMA–CCL) as macroactivators and sodium caprolactamate as catalyst. Three grades of PMMA–CCLs obtained by free radical copolymerization were used for synthesizing the PMMA-g–PA6 copolymers with different PMMA content. The resulting graft copolymer was characterized by Fourier-transform infrared spectroscopy and selective extraction. Scanning electron microscopy is used to clarify the phase morphology of obtained polymer by fracture surface. The thermal property, crystallinity and dimensional stability of graft copolymer were studied using differential scanning calorimetry, X-ray diffraction and water absorption measurement. The results show the T_g of graft copolymer is higher than that of neat PA6, but the onset and peak points of graft copolymer melting point are shifted to lower temperature. The percentage crystallinity and water absorption of PMMA-g–PA6 copolymer decrease with increasing PMMA content, but the crystal structure of PA6 is scarcely affected by the presence of PMMA. Graft copolymers have improved dimensional stabilities relative to neat PA6. Upon the incorporation of 19.9 wt% PMMA into PA6, the water absorption of PMMA-g–PA6 copolymer has been reduced from 4.8 for neat PA6 to 2.1%.     

Dynamic viscoelastic behavior of cholesteric liquid crystalline side-chain copolymers

Summary The rheological behavior of the cholesteric side-chain copolysiloxane whose two kinds of mesogenic groups consist of cholesteryl units and biphenyl benzoate units was investigated for three different compositions: 31:69, 35:65, 37:63 (in mol%). On the frequency dependence diagram of G′ for the copolymers at various temperatures, G′ decreases with decreasing frequency. The slope of G′ in a higher frequency region at lower temperatures (110°–130°C) is similar to that in the flow region of amorphous polymer melts. However, the slope of G′ in a lower frequency region at higher temperatures (140°–160°C) is relatively small, and the G′ curves in this region can not be superposed on to a single master curve. This deviation seems to be due to change in stability of the domain structure of the cholesteric phase. Furthermore, on the temperature dependence curve of G′, G′ showed a maximum near T _c1 . This maximum of G′ curve seems to be caused by molecular organization of a blue phase.     

Fusion-cast chromium-bearing refractories — the most durable materials in aggressive melts

Information is presented on fusion-cast materials that have been developed in recent years on the basis of the systems Cr₂O₂–Al₂O₃–ZrO₂–SiO₂, Cr₂O₃–MgO–SiO₂, and Cr₂O₃–MgO–Al₂O₃. Such materials have good service properties in mineral melts at high temperatures. It is shown that fusion-cast chromium-bearing refractories KhPL-85 and KhMG are as corrosion-resistant as chromium-oxide-based ceramic refractories in melts of alkali-free borosilicate glass E and basalt fibers.     

Morphology evolution of immiscible polymer blends as directed by nanoparticle self-agglomeration

This work aims to clarify the effect of nanoparticle self-agglomeration structure on the morphology of polymer blends. The morphology development of polystyrene (PS)/polyamide (PA6) blends with titanium dioxide (TiO₂) nanoparticles preferentially localized in the PA6 domains was investigated by means of electron microscopy observation, viscoelastic analysis and selective extraction tests. It was shown that the preferential dispersion of TiO₂ leads to a significant reduction of the PA6 continuity in the PS/PA6 blend. The size of the PA6 domain increases gradually with further increasing the nanoparticle loading whereas the co-continuity of the PS/PA6/TiO₂ mixture is destroyed by isothermal post-treatments. These experimental results are completely different from those in carbon black, nanoclay or nano-silica-filled immiscible polymer blends. To elucidate the progression to the uneven morphology change, the dynamic process of microfibril break-up and droplet coalescence in the molten PS/PA6/TiO₂ mixture was traced in real-time through optical microscopy. It was confirmed that the self-agglomerating pattern of the nanoparticle in the polymer melts plays a key role in directing the morphology evolution of the immiscible polymer blend: unlike the self-agglomeration of carbon black to form three-dimensionally continuous network structure, the TiO₂ nanoparticles tend to form separate clusters in the PA6 phase. This prevents PA6 droplets from fusing together to form a continuous network during the coalescence and producing larger PA6 domains at higher TiO₂ loads.     

Hyperbranched azo polyurethane synthesized through A2 + B3 scheme

A hyperbranched azo polyurethane was synthesized by one-step polymerization of an A₂ type monomer diphenylmethane-4,4′-diisocyanate and a B₃ type monomer 4-(N,N′-bis(2-hydroxyethyl))amino-2′-hydroxyethoxyl-4′-nitro-azobenzene. The azo polymer was characterized by ¹H nuclear magnetic resonance (NMR), ultraviolet-visible (UV-Vis) spectrum and thermal analysis. The λ_max of the polymer in dimethylformamide (DMF) solution is 488 nm. The number average molecular weight (M_n) determined by GPC is 9,300 with a polydispersion index 1.9. The glass transition temperature (T _g) of the polymer is 131°C observed from DSC thermogram. The results show that the azo polyurethane has been successfully synthesized through this scheme. Surface-relief-gratings (SRGs) were fabricated on the polymer film after being irradiated by interference pattern of Ar⁺ laser beams for 1,000 s. The surface modulation depth and the grating space period measured by AMF are 67 and 770 nm, respectively. __________ Translated from Acta Polymerica Sinica, 2007, 1: 21–25 [译自: 高分子学报]     

Study on the preparation of Mg–Li–Mn alloys by electrochemical codeposition from LiCl–KCl–MgCl<Subscript>2</Subscript>–MnCl<Subscript>2</Subscript> molten salt

This study presents a novel electrochemical study on the codeposition of Mg, Li, and Mn on a molybdenum electrode in LiCl–KCl–MgCl₂–MnCl₂ melts at 893 K to form different phases Mg–Li–Mn alloys. Transient electrochemical techniques such as cyclic voltammetry, chronopotentiometry, and chronoamperometry have been used in order to investigate the codeposition behavior of Mg, Li, and Mn ions. The results obtained show that the potential of Li metal deposition, after the addition of MgCl₂ and MnCl₂, is more positive than the one of Li metal deposition before the addition. The codeposition of Mg, Li, and Mn occurs at current densities lower than −1.43 A cm⁻² in LiCl–KCl–MgCl₂ (8 wt%) melts containing 2 wt% MnCl₂. The onset potential for the codeposition of Mg, Li, and Mn is −2.100 V. α, α + β, and β phases Mg–Li–Mn alloys with different lithium and manganese contents were obtained via galvanostatic electrolysis from LiCl–KCl melts with different concentrations of MgCl₂ and MnCl₂. The microstructures of typical α and β phases of Mg–Li–Mn alloys were characterized by X-ray diffraction (XRD), optical microscopy (OM), and scanning electron microscopy (SEM). The analysis of energy dispersive spectrometry (EDS) and EPMA area analysis showed that the elements of Mg and Mn distribute homogeneously in the Mg–Li–Mn alloys. The results of inductively coupled plasma analysis determined that the chemical compositions of Mg–Li–Mn alloys correspond with the phase structures of XRD patterns, and lithium and manganese contents of Mg–Li–Mn alloys depend on the concentrations of MgCl₂ and MnCl₂.     

Mixing and Spinnability of Polymer Blends on the Example of the Polyamide 6.6—Poly(Ethylene Terephthalate) Model System

The method of combined evaluation of the quality of mixing and the quality of a polymer blend allows predicting the character of the change in the disperse structure of the blend when the extrusion process parameters change. The spinnability criterion, which is the ratio of the parameters of the extruder deformation field — ratio of shear strains (average and minimum, determined in the section @zeta;₃), prespinneret, and spinneret drawing, allows explaining the change in the spinnability of PA6.6—PET polymer blend melts when the process parameters change from unified positions.     

Electrochemical study of the codeposition of Mg–Li–Al alloys from LiCl–KCl–MgCl<Subscript>2</Subscript>–AlCl<Subscript>3</Subscript> melts

This work presents a novel electrochemical study on the codeposition of Mg, Li and Al on a molybdenum electrode in LiCl–KCl–MgCl₂–AlCl₃ melts at 943 K to form Mg–Li–Al alloys. Cyclic voltammograms (CVs) showed that the underpotential deposition (UPD) of magnesium on pre-deposited aluminum leads to the formation of a liquid Mg–Al solution, and the succeeding underpotential deposition of lithium on pre-deposited Mg–Al leads to the formation of a liquid Mg–Li–Al solution. Chronopotentiometric measurements indicated that the codeposition of Mg, Li and Al occurs at current densities lower than −0.47 A cm⁻² in LiCl–KCl–MgCl₂ (0.525 mol kg⁻¹) melts containing 0.075 mol kg⁻¹ AlCl₃. Chronoamperograms demonstrated that the onset potential for the codeposition of Mg, Li and Al is −2.100 V, and the codeposition of Mg, Li and Al is formed when the applied potentials are more negative than −2.100 V. The diffusion coefficient of aluminum ions in the melts was determined by different electrochemical techniques. X-ray diffraction and inductively coupled plasma analysis indicated that α, α + β and β Mg–Li–Al alloys with different lithium and aluminum contents were obtained via potentiostatic and galvanostatic electrolysis.     

Synthesis of poly-p-phenylenebenzobisthiazole used for fabrication of a thermostable, high-modulus fibre

A method was developed for synthesis of poly-p-phenylenebenzobisthiazole (PPBT) from 2,5-diamino-1,4-dimercaptobenzene diphosphate (DADMB) and terephthalic acid (TPA) in a solution of polyphosphoric acid (PPA) with a 12–15 wt. % concentration of PPBT with a molecular weight of 34,000–38,600 ([η] = 24.5–28.8 dl/g). It was shown that a high concentration of P₂O₅ in PPA, which should be 85.5–86.5 wt. % at the end of the reaction, is one of the basic conditions for obtaining a high-molecular-weight polymer from DADMB diphosphate and TPA. The synthesized liquid-crystalline polymers with a high molecular weight and concentration of 14–15 wt. % in PPA solution were used in the form of polycondensation solutions for spinning high-modulus PPBT fibres. Translated fromKhimicheskie Volokna, No. 6, pp. 35–39, November–December, 1998. We would like to thank L. P. Mil'kova for participating in the x-ray diffraction studies and discussing the results.     

Development of technology for the production of microspherical alumina support for the alkane dehydrogenation catalyst: III. The effect of the phase composition of microspherical supports on their thermal stability

This publication continues a series of our reports on the optimization of preparation conditions for obtaining a thermally stable support for the alkane dehydrogenation catalyst. The phase composition effect on the stability, particle size distribution, structure, texture, and mechanical properties of supports heated to 1100°C is reported. Microspherical alumina supports obtained by successive thermal and hydrothermal treatments of gibbsite are compared to commercial supports obtained by the thermochemical activation (TCA) of gibbsite. The dimensions of the support granules decrease upon heating because of shrinkage, which is governed by the phase composition of the granules and by the packing of their constituent boehmite and alumina crystallites. Three temperature intervals can be distinguished in the shrinkage of the granules. In region I (<600°C), there is intensive shrinkage via the diffusion glide of crystallites, the mechanical strength of the granules remaining invariable. In region II (600–900°C), the polymorphic transformations of alumina accompanied by sintering via surface diffusion do not affect the dimensions and strength of the granules. In region III (>900–1000°C), shrinkage takes place via coalescent sintering. For commercial manufacturing of microspherical alkane dehydrogenation catalysts and for ensuring their stability at 550–900°C, it is recommended to use alumina supports containing the minimum possible amount of χ-Al₂O₃. As the single-phase boehmite support obtained by our technology is heated to 1100°C, its granules shrink by no more than 14.4% and show an attrition resistance of 89% or above. The support based on the gibbsite TCA products, which contains 14–23 wt % χ-Al₂O₃, is characterized by 3–5% greater granule shrinkage and 6–12% lower mechanical strength.     

Analysis of disproportionation of <Emphasis Type="Italic">Q</Emphasis><Superscript><Emphasis Type="Italic">n</Emphasis></Superscript> structons in the simulation of the structure of melts in the Na<Subscript>2</Subscript>O-SiO<Subscript>2</Subscript> system

A new version of the STRUCTON-1.2 computer program (2009) has been presented. The program combines the algorithm for calculating real distributions of Q ⁿ structons in binary silicate melts (with allowance made for their disproportionation) and the statistical simulation of molecular-mass distributions of polymerized ions at different temperatures. This model has been used to perform test calculations for two melts in the Na₂O-SiO₂ system (Na₆Si₂O₇, Na₆Si₃O₉). The results of the calculations have made it possible to trace variations in the set and concentrations of chain and ring silicon-oxygen complexes with a decrease in the temperature in the order: stochastic molecular-mass → distribution molecular-mass distribution at T = 2000 K → molecular-mass distribution at the liquidus temperature. The main result of these calculations is that the dominant species of silicon-oxygen anions at the liquidus temperatures (in contrast to the stochastic distributions) exactly correspond to the stoichiometry of the initial melts: the Si₂O₇⁶⁻ chain anions and (Si _n O_3n )³ⁿ⁻ ring complexes are dominant in the Na₆Si₂O₇ and Na₆Si₃O₉ melts, respectively. It has been established that, with a decrease in the temperature, the average size of polymer complexes varies weakly in the Na₆Si₂O₇ melt but increases by a factor of approximately 1.5 in the metasilicate system.     

Interaction between water vapor and welding fluxes according to the polymer theory

Water vapor dissolution in the slag melt model introduced in the paper is based on polymer theory. Calculated data on water dissolution in CaF₂-CaO-SiO₂ system melts are presented and compared with the experimental data. The results can be used for mathematical modeling of physicochemical processes of submerging arc welding and special electro-metallurgy. This paper was presented at the Topical Meeting of the European Ceramic Society “Structural Chemistry of Partially Ordered Systems, Nanoparticles, and Nanocomposites,” St. Petersburg, Russia, June 27–29, 2006. The text was submitted by the authors in English.     

Synthesis, Characterization, Conductivity, Band Gap, and Thermal Analysis of Poly-[(2-mercaptophenyl)iminomethyl]-2-naphthol and Its Polymer–Metal Complexes

Oxidative polycondensation reaction conditions of [(2-mercaptophenyl)iminomethyl]-2-naphthol (2-MPIM-2N) were studied using oxidants such as air and NaOCl in an aqueous alkaline medium between 40 °C and 90 °C. The structure of poly-[(2-mercaptophenyl)iminomethyl]-2-naphthol (P-2-MPIM-2N) was characterized by ¹H- ¹³C NMR, FT-IR, and UV–Vis spectroscopy, size exclusion chromatography (SEC), and elemental analysis. At optimum reaction conditions, the yield of P-2-MPIM-2N was found to be 78 and 82% for air and NaOCl oxidants, respectively. From SEC measurements, the number-average molecular weight (M _n ), weight-average molecular weight (M _w ) and polydispersity index (PDI) of P-2-MPIM-2N are 2900, 3500 g mol⁻¹ and 1.207; 2200, 2500 g mol⁻¹ and 1.136, for air and NaOCl oxidants, respectively. Polymer–metal complexes were synthesized by the reaction of P-2-MPIM-2N with Co²⁺, Cu²⁺, Zn²⁺, Pb²⁺ and Cd²⁺ ions. The highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and electrochemical band gaps (E^￠_g E^{\prime}_{g} ) of 2-MPIM-2N and P-2-MPIM-2N were −5.97, −2.66 and 3.31 eV and −5.82, −2.68 and 3.14 eV, respectively. The conductivity of polymer and polymer–metal complexes were determined in the solid state. Conductivity measurements of doped and undoped Schiff base polymer and polymer–metal complexes were carried out at room temperature and atmospheric pressure by the four-point probe technique using an electrometer. The conductivities of the polymer and polymer–metal complexes increased when iodine was used as doping agent.     

Electrochemical investigation of Al–Li/Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>FePO<Subscript>4</Subscript> cells in oligo(ethylene glycol) dimethyl ether/LiPF<Subscript>6</Subscript>

1 M LiPF₆ dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight, 500 g mol⁻¹ (OEGDME500, 1 M LiPF₆), was investigated as an electrolyte in experimental Al–Li/LiFePO₄ cells. More than 60 cycles were achieved using this electrolyte in a Li-ion cell with an Al–Li alloy as an anode sandwiched between two Li _x FePO₄ electrodes (cathodes). Charging efficiencies of 96–100% and energy efficiencies of 86–89% were maintained during 60 cycles at low current densities. A theoretical investigation revealed that the specific energy can be increased up to 15% if conventional LiC₆ anodes are replaced by Al–Li alloy electrodes. The specific energy and the energy density were calculated as a function of the active mass per electrode surface (charge density). The results reveal that for a charge density of 4 mAh cm⁻² about 160 mWh g⁻¹ can be reached with Al–Li/LiFePO₄ batteries. Power limiting diffusion processes are discussed, and the power capability of Al–Li/LiFePO₄ cells was experimentally evaluated using conventional electrolytes.     

Synthesis of poly(ethyl vinyl ethers) containing two dipolar electronic systems and their properties

Summary 5-Nitro-2-(2′-vinyloxyethoxy)benzylidenemalononitrile (2a), methyl 5-nitro-2-(2′-vinyloxyethoxy)benzylidenecyanoacetate (2b), 3-nitro-4-(2′-vinyloxyethoxy)benzylidenemalononitrile (4a), and methyl 3-nitro-4-(2′-vinyloxyethoxy)benzylidenecyanoacetate (4b) were prepared by the condensation of 5-nitro-2-(2′-vinyloxyethoxy)benzaldehyde (1) and 3-nitro-4-(2′-vinyloxyethoxy)benzaldehyde (3) with malononitrile or methyl cyanoacetate, respectively. Vinyl ether monomers 2a-b and 4a-b were polymerized with boron trifluoride etherate as a cationic initiator to yield poly(vinyl ethers) 5-6 having nitrooxybenzylidenemalononitrile and nitrooxycyanocinnamate, which is effective chromophore for second-order nonlinear optical applications. Polymers 5-6 were soluble in common organic solvents such as acetone and DMSO. T _g values of the resulting polymer were in the range of 70–81°C. Electrooptic coefficient (r₃₃) of the poled polymer films were in the range of 19–27 pm/V, which was improved by introducing of nitro group. Polymers 5–6 showed a thermal stability up to 300°C in TGA thermograms, which is acceptable for NLO device applications. Received: 24 November 1998/Revised version: 19 January 1999/Accepted: 29 January 1999     

Synthesis of semiconducting polyphenylacetylene catalyzed by Ni(MeCN)6(BF4)2/AlEt2Cl

Summary Phenylacetylene (PhA) is polymerized by the dicationic nickel complex Ni(MeCN)₆(BF₄)₂ associated with AlEt₂Cl as co-catalyst. The production of 200g of polymer per gram of nickel per hour represents a typical activity of this system. Under our experimental conditions, the polymer displays an exclusive trans structure. The molecular weight distribution of the polymer is polymodal (5000 g.mol⁻¹ and 200 g.mol⁻¹). The highest average molecular weight fraction (5000 g. mol⁻¹) represents the highest published value for polyphenylacetylene (PPA) where a nickel catalyst is employed. The electrical conductivities vary between 10⁻⁷ and 10⁻¹⁶ S.cm⁻¹, and are characteristic of a semi-conductor polymer. Equivalent values are cited in the literature only in the case of doped PPA. Experimental observations enabled us to propose a mechanism for the formation of the active species through the reaction of Ni(MeCN)₆(BF₄)₂ with AlEt₂Cl. Received: 13 September 2001/Revised version: 10 January 2002/ Accepted: 11 January 2002     

Ring-opening polymerization of (CH3)2Si[CpMo(CO)3]2, a molecule with an –Si(CH3)2– bridge between two cyclopentadienyl ligands

The (CH₃)₂Si[CpMo(CO)₃]₂ complex (1) was synthesized and used to explore ring-opening polymerization (ROP) as a method to prepare high molecular weight polymers containing Mo–Mo bonds along their backbones. Attempts to initiate ROP of 1 using n-BuLi or PtCl₂ did not yield any polymers. The X-ray crystal structure of 1 shows that the Si center is not strained, and it is suggested that no ROP occurred because 1 is less strained than other organometallic ROP monomers, such as the silicon-bridged ferrocenophanes. Thermal ROP (TROP) of 1 was successful and yielded a polymer (M _w = 210,000 g mol⁻¹) containing both Mo–Mo single bonds and Mo≡Mo triple bonds. When CO_(g) is passed over the polymer in the solid state, the Mo≡Mo triple bonds are converted to Mo–Mo single bonds. Attempts to increase the yield of the TROP polymer by increasing the reaction times led to polymer decomposition. The decomposition is likely caused by the weakness of the Mo–Mo bond, cleavage of which causes the polymer to degrade.     

Adsorption of carbon dioxide on ionic liquids-modified active carbons and amino-modified polymer

Active carbons with various particle sizes (38–150, 300–500 and 800–1,200 μm) were modified by ionic liquids (ILs), and organic polymer was modified by acrylamide using a simple procedure, and these materials were applied to capture carbon dioxide (CO₂). The CO₂ adsorption amounts were calculated using a mass balance equation at three different temperatures (298.15, 308.15 and 318.15 K), respectively, and the influences of gas pressure, particle size and temperature on adsorption were discussed. Experimental results showed that the CO₂ adsorption capacity of ILs-modified active carbons was better than amino-modified polymer, and the smaller particle size (38–150 μm) ILsmodified active carbons had the largest adsorption capacity at 298.15 K. Compared with previous research about polyethyleneimine (PEI)-modified silica gel, the adsorption amount of CO₂ on ILs-modified active carbons has been greatly improved with lower cost.     

Flow of polymer systems in the viscoelastic state through round capillaries. A rheological analysis

Steady-state flow ofpolymer systems (polymer melts and solutions) in the viscoelastic state is considered the superposition of two processes — flow of a viscous fluid and extrusion of an elastic fluid (elastic state). The dynamic elasticity is proposed for characterizing the elastic properties of polymer systems, and the complex viscosity, which is the total value of the dynamic elasticity and the dynamic viscosity, widely used for assessing viscous properties, is proposed for characterizing the generalized properties, by analogy with periodic deformation. __________ Translated from Khimicheskie Volokna, No. 1, pp. 3–6, January–February, 2006.     

Semicontinuous heterophase polymerization of methyl methacrylate in the presence of reactive surfactant HITENOL BC10

Semicontinuous heterophase polymerization was used to copolymerize methyl methacrylate (MMA) with reactive surfactant HITENOL BC10 (HBC10) at 60 °C using sodium dodecyl sulfate as pre-stabilizing agent and potassium persulfate as initiator. The mixture of MMA and HBC10 was added at constant rate in continuous mode varying the MMA/HBC10 ratio. High-polymerization rates were observed, decreasing as the MMA/HBC10 ratio decreased. Latexes with polymer content near 20% and polymer to surfactant (P/S) weight ratios between 5 and 15 were obtained. Particle sizes distribution were bimodal in all cases with a tendency to be monomodal as HBC10 concentration increased which was ascribed to enhanced particle stabilization by the presence of HBC10. The average particle diameters at the end of polymerizations for the first and second populations were around 10 and 50 nm, respectively. Very high average molecular weights were observed (1.4 × 10⁶ ≤ M _w  ≤ 2.1 × 10⁶ g/mol), which decreased when HBC10 concentration increased. The corresponding polydispersity indexes (M _w /M _n ) were in the range of 1.45–2.24.