The ATRP Synthesis of the Potential Thermoplastic Elastomer Poly(methyl methacrylate)–b-(lauryl methacrylate)-b-(methyl methacrylate) Hitherto Unrealized by Ionic Polymerization

The triblock copolymer poly(methyl methacrylate-b-lauryl methacrylate-b-methyl methacrylate) {P(MMA-b-LMA-b-MMA)} has been synthesized by a two stage atom transfer radical polymerization in bulk at near room temperature (ca. 35 °C) using CuCl/pentamethyldiethylenetriamine (PMDETA)/tricaprylylmethylammonium chloride (Aliquat®336) complex as the catalyst and 1,2-bis (bromoisobutyryloxy)ethane (BIBE) as the initiator for the polymerization of LMA in the first stage. The same catalyst was also used for the polymerization of MMA in the second stage. The dynamic mechanical thermal analysis of a sample with the middle block M_n = 82000 and each end block M_n = 14500 showed typical features of a thermoplastic elastomer.     

Phase behavior and modeling of the poly(methyl methacrylate)–CO2–methyl methacrylate system

Cloud-point data for the system poly(methyl methacrylate) (PMMA)–CO₂–methyl methacrylate (MMA) are measured in the temperature range of 26 to 170°C, to pressures as high as 2500 bar, and with cosolvent concentrations of 10.4, 28.9, and 48.4 wt.%. PMMA does not dissolve in pure CO₂ to 255°C and 2550 bar. The cloud-point curve for the PMMA–CO₂–10.4 wt.% MMA system exhibits a negative slope that reaches 2500 bar at 105°C. With 28.9 wt.% MMA the cloud-point curve remains relatively flat at ∼900 bar for temperatures between 25 and 170°C. With 48.4 wt.% MMA the cloud-point curve exhibits a positive slope that extends to 20°C and ∼100 bar. Pressure-composition isotherms are also reported for the CO₂–MMA system at 40.0, 80.0, 105.5°C. This system exhibits type-I phase behavior with a continuous mixture–critical curve. The Peng–Robinson (PR) and SAFT equations of state model the CO₂–MMA data reasonably well without any binary interaction parameters, although the PR equation provides a better representation of the mixture-critical region. It is not possible to obtain even a qualitative fit of the PMMA–MMA–CO₂ data with the SAFT equation of state. The SAFT model qualitatively shows that the cloud-point pressure decreases with increasing MMA concentration and that the cloud-point curve exhibits a positive slope for very high concentrations of MMA in solution.     

Studies of aminolysis of acrylonitrile–divinylbenzene–methyl methacrylate copolymers

Aminolysis of nitrilacrylate–divinylbenzene–methyl methacrylate copolymers by diethylenetriamine is studied under various conditions. The effect of temperature and catalyst concentration on the properties of synthesized anion exchangers depending on the duration of aminolysis is investigated. The conditions for synthesizing anion exchangers with high capacity characteristics are proposed according to the study results.     

Subsurface oxygen in monomer–dimer catalytic reaction: Influence of second and third nearest neighbourhood

The presence of subsurface species adds two extra steps to the usual four of simple Langmuir Hinshelwood mechanism of the monomer–dimer (NO–CO) surface reaction. In this model the influence of second and third nearest neighbouring (nn) sites on the phase diagram of the system is studied in detail by the use of Monte-Carlo simulation. It is seen that reaction between surface second nn sites has more dominant effect on the width of the reactive window as compared to that of subsurface second and third nn sites. In another model, NO is adsorbed in such a way that N takes surface site whereas O takes its subsurface first nn site. In this model the reaction of CO with subsurface second and third nn sites gives an interesting situation: The usual second-order phase transition is destroyed and consequently a very wide steady reactive window is observed.     

Catalytic and inhibiting effects of ferrocene on the bulk radical–coordination polymerization of methyl methacrylate from the standpoint of formal kinetics

The kinetic curves and rates of bulk radical–coordination polymerization of methyl methacrylate initiated by the benzoyl peroxide–ferrocene system at 293–373 K, initial benzoyl peroxide concentrations of 10^–4–10^–1 mol/L, and a constant initial ferrocene concentration of 10^–3 mol/L have been calculated using a mathematical model in which the process is considered from the standpoint of formal kinetics. The calculations have demonstrated that, at low methyl methacrylate conversions, ferrocene catalyzes the process at any benzoyl peroxide concentration; at medium and high methyl methacrylate conversions, deficient amounts of ferrocene with respect to benzoyl catalyze the process as well, while excess ferrocene inhibits the process. The observed effect is explained by the specific ferrocene–benzoyl peroxide interaction, which, depending on the ferrocene: benzoyl peroxide ratio, either increases or decreases the concentration of radicals in the reaction mass.     

Influence of α-Fe2O3 nanorods on the thermal stability of poly(methyl methacrylate) synthesized by in situ bulk polymerisation of methyl methacrylate

α-Fe₂O₃ nanorods were incorporated into poly(methyl methacrylate) (PMMA) by in situ radical polymerisation of methyl methacrylate initiated by 2,2′-azobisisobutyronitrile. The α-Fe₂O₃ nanorods were synthesized by forced hydrolysis of FeCl₃ and structural characterization was performed by X-ray diffraction and transmission electron microscopy. The molar mass and the polydispersity index of synthesized PMMA samples were determined by gel permeation chromatography. The content of residual monomer was determined by ¹H NMR spectroscopy. The influence of α-Fe₂O₃ nanorods on the thermal stability of the polymer was investigated using thermogravimetry and differential scanning calorimetry. The molar mass and polydispersity index of PMMA were dependent on the content of α-Fe₂O₃ nanorods. The values of the glass transition temperature of the nanocomposites were lower compared to pure PMMA. Also, the thermal stability of nanocomposites in nitrogen and air was different from that of pure PMMA.     

An Observation on the Microphase Separation of Poly(methyl methacrylate)-block-Polystyrene Copolymer

The well-ordered structures of block copolymer formed by self-assemble have attracted much attention as potentially interesting optical materials, especially as photonic crystals1,2. In order to achieve desirable photonic crystal properties, the morphologies of block copolymers should be controlled, including obtaining the correct size of domains for the optical frequencies of interest and attainment of long-range domain order and appropriate orientation. We know that the morphology of one blo…     

Photopolymerization of methyl methacrylate in the presence of the tri-n-butyl boron—p-quinone system

The photopolymerization of methyl methacrylate in the presence of tri-n-butyl boron and a number of p-quinones is studied in a wide concentration range. It is shown that the rate of polymerization and the molecular-mass characteristics of the polymers depend on the structure and concentration of p-quinone. PMMA isolated at various conversions initiates the secondary polymerization of methyl methacrylate. The activity of the macroinitator depends on the structure of p-quinone.     

Preparation and characterization of novel thermal-stable vinylidene chloride–methyl acrylate–glycidyl methacrylate copolymer

A novel copolymer was synthesized by vinylidene chloride (VDC)/methyl acrylate (MA)/glycidyl methacrylate (GMA). The Fourier transform infrared (FTIR) and ¹H-nuclear magnetic resonance analyses indicated that the copolymer of VDC/MA/GMA (PVMG) was synthesized successfully. The influences of GMA on the molecular weight, melting point, and thermal stability of copolymer were investigated by gel permeation chromatograph, differential scanning calorimeter, thermogravimetric analysis–FTIR, respectively. The copolymerization eliminated the phenomenon of “double melting peaks” for poly(vinylidene chloride), and the melting point was reduced to 165°C. The GMA also enhanced the thermal stability of copolymer, which was proved by the increased decomposition temperature of copolymer. The existence of GMA caused the cross-linking of the copolymer, which contributed to the improvement of barrier performance of PVMG.     

Fabrication, characterization, and supercooling suppression of nanoencapsulated n-octadecane with methyl methacrylate–octadecyl methacrylate copolymer shell

Supercooling of micro- and nanoencapsulated phase change material is widely observed as their diameters depress to a limitation upon cooling. The aim of this study is to suppress the supercooling of nanoencapsulated n-octadecane (NanoC18) using a novel copolymer consisting of long n-alkyl side chains as shell. Nanoencapsulations of n-octadecane with various compositions of poly(methyl methacrylate-co-octadecyl methacrylate) copolymer as shells were carried out by means of miniemulsion polymerization. Fabrication, morphology, diameter distributions, phase change behaviours, and thermal stabilities of nanocapsules were investigated using Fourier transformed infrared spectroscopy, a field-emission scanning electron microscope, a transmission electron microscope, particle size distribution analysis, differential scanning calorimetry, and thermogravimetric analysis. The results indicate that a series of nanocapsules with core/shell structure and spherical shapes are fabricated with average diameters ranging from 373 to 398 nm. The average thickness of the shells is about 60 nm. All the NanoC18 crystallize into a stable triclinic phase via a metastable rotator phase (R_I) from the liquid phase. The crystallization temperature of n-octadecane within poly(methyl methacrylate) nanocapsules is considerably lower than that in bulk phase. Supercooling is effectively suppressed using the comb-like copolymer with crystallizable n-octadecyl side chains as shell. Octadecyl methacrylate is not only employed as a reactive costabilizer to suppress the influence of Ostwald ripening during the formation of nanocapsules but also as a functional monomer in the composition of the copolymer shell in order to suppress the supercooling of NanoC18.     

Influence of the zirconia transformation on the thermal behavior of zircon–zirconia composites

During a heating?Ccooling cycle, zirconia (ZrO₂) undergoes a martensitic transformation from monoclinic to tetragonal structure phases, which presents special hysteresis loop in the dilatometry curve at temperatures between 800 and 1100?°C. Monoclinic zirconia (m-ZrO₂) particles reinforced ceramic matrix composites not always present this behavior. In order to elucidate this fact a series of zircon?Czirconia (ZrSiO₄?CZrO₂) ceramic composites have been obtained by slip casting and characterized. The final properties were also correlated with the zirconia content (0?C30?vol.%). The influence of the martensitic transformation (m?Ct) in well-dispersed zirconia grains ceramic composite on the thermal behavior was analyzed. Thermal behavior evaluation was carried out; the correlation between the thermal expansion coefficients with the zirconia content showed a deviation from the mixing rule applied. A hysteresis loop was observed in the reversible dilatometric curve of composites with enough zirconia grains (??10?vol.%). Over this threshold the zirconia content is correlated with the loop area. The transformation temperatures were evaluated and correlated with the zirconia addition. When detected the m?Ct temperature transformation is slightly influenced by the zirconia content (due to the previously evaluated decrease in the material stiffness) and similar to the temperature reported in literature. The reverse (cooling) transformation temperature is strongly decreased by the ceramic matrix. The DTA results are consistent with the dilatometric analysis, but this technique showed more reliable results. Particularly the endothermic m?Ct transformation temperature showed to be easily detected even when the only m-ZrO₂ present was the product of the slight thermal dissociation of the zircon during the processing of the pure zircon material.     

Influence of synthetic perfumes on stability of O/W emulsion in sodium dodecyl sulfate–n-dodecane–water ternary systems

Influence of synthetic perfumes having diverse chemical structures such as eugenol, linalool, benzyl acetate, α-ionone, α-hexylcinnamaldehyde, and d-limonene on stability of oil-in-water (O/W) emulsion composed of sodium dodecyl sulfate, n-dodecane, and water is investigated. Turbidity measurements of the O/W emulsion indicate that the emulsion is stabilized by adding the synthetic perfume, except for d-limonene, and that this tendency is remarkable in adding eugenol. The addition of the perfume, especially eugenol, shrinks oil droplets in the O/W emulsion, which inhibits coagulation and/or creaming of oil droplets. When adding eugenol, moreover, ζ-potential of oil droplets increases negatively, and viscosity of the external water phase of the emulsion rises drastically. The increment in ζ-potential and viscosity by the addition of eugenol also prevents oil droplets from coagulation and/or creaming and makes the O/W emulsion still more stable.     

Influence of the anisometry of magnetic particles on the isotropic–nematic phase transition

The influence of the shape anisotropy of magnetic particles on the isotropic–nematic phase transition was studied in ferronematics based on the nematic liquid crystal (LC) 4-(trans-4-n-hexylcyclohexyl)-isothiocyanato-benzene (6CHBT). The LC was doped with spherical or rod-like magnetic particles of different size and volume concentrations. The phase transition from isotropic to nematic phase was observed by polarising microscope as well as by capacitance measurements. The influence of the concentration and the shape anisotropy of the magnetic particles on the isotropic–nematic phase transition in LC are demonstrated here. The results are in a good agreement with recent theoretical predictions.     

Influence of Fe concentration on the properties of the electrodeposited Zn–Fe coatings

Electrodeposition of Zn–Fe alloys on a copper substrate from a sulfate bath with different Fe²⁺ concentration (0.05, 0.10 and 0.20 mol L^?1) at room temperature was investigated using cyclic voltammetry. The influence of the Fe²⁺ content in the plating bath on the surface morphology, structural and magnetic properties of the coatings were characterized using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and Vibrating Sample Magnetometer (VSM). The results show that the morphology of Zn–Fe films changes with different Fe²⁺ concentration. The EDS analysis demonstrated that the Fe content of the coatings increased with increasing the Fe concentration in the bath. XRD measurements shows the presence of ?Zn (hcp), δ1ZnFe (hcp) and the ΓZnFe (bcc) phases with a (101) preferential orientation in all the electrodeposited films. The magnetic analysis of Zn–Fe films indicated that the saturation magnetization was largely enhanced in comparison to pure Zn, especially with 0.2 at. % Fe, while the coercivity decreased.     

Influence of monomer concentration on polycarbazole–polyindole (PCz–PIn) copolymer properties: Application in Schottky diode

Copolymerization of carbazole (Cz) and indole (In) is successfully performed through potentiostatic polymerization; and the influence of the monomer concentrations ratio on copolymer formation, is investigated. It is found that 1:2 ratio of Cz to In monomer is optimum for the synthesis of a copolymer with high electroactivity. The structural, optical, thermal and morphological analysis of the copolymers are carried out with UV–vis, FT–IR spectroscopy, differential scanning coulometry (DSC) and scanning electron microscopic (SEM) technique. Electrochemical and thermal studies, further support better redox activity and thermal stability of the copolymer, respectively. We also report fabrication and characterizations of the electrochemically synthesized copolymer in organic Schottky diode with configuration metal Al/copolymer/indium tin oxide coated glass (ITO). The current density–voltage (J–V) characteristic of the Schottky diode is consequential in extracting the electronic parameters and the charge transport mechanism of the devices.     

Influence of Sr addition on microstructure of the hypereutectic Zn–Al–Cu alloy

Journal of Thermal Analysis and Calorimetry - The purpose of the presented work is to answer the questions: how does the addition of strontium to the Zn–8Al–1Cu alloy crystallisation...     

Influence of fibre–fibre joint properties on the dimensional stability of paper

Measurements have been performed to clarify the connection between fibre–fibre joint properties and dimensional stability using laboratory sheets prepared from never-dried fibres, from heavily hornified fibres having a low molecular contact area between the fibres, and from both hornified and never-dried fibres treated with a polyelectrolyte multilayer (PEM) technique to increase the molecular contact area in the fibre–fibre joint. The influence of the drying mode, i.e. whether the sheets are dried freely or under restraint, was also evaluated. The results showed that neither paper strength nor fibre–fibre joint contact area had any significant influence on the dimensional stability of sheets dried under restraint. On the other hand, when the sheets were dried freely, the PEM-treated sheets expanded to the same extent as, or to an even greater extent than the non-PEM-treated sheets, even though they adsorbed less water for a given change in relative humidity. There was also a correlation between drying shrinkage and dimensional stability, where greater shrinkage was associated with a greater hygroexpansion in the freely dried sheets.     

Influence of the synthesis parameters on the thermal behavior of some ZnO–starch composites

Ten ZnO–starch composites were synthesized using a simple precipitation methodology. The IR spectroscopy and XRD investigations reveal the presence of amorphous starch and crystalline ZnO. The obtained composites present a spherical morphology, 5–8 spheres being interconnected into aggregates. The thermal analysis demonstrates that starch decomposition and ZnO thermally induced nucleation and crystal growth depending on the synthesis parameters such as starch processing (dissolution or gelatinization), reaction temperature (80, 90, and 100 °C), reaction time (15 min or 6 h), and applied treatments (heating or ultrasound irradiation).     

Influence of Cyclodextrin on the Styrene Polymerization

Cyclodextrin (CD) are oligosaccharides consisting of 6(α), 7(β), 8(γ) units of 1,4-linked glucose. Due to their polar hydrophilic outer shell and relatively hydrophobic cavity, they are able to build up host-guest complexes by inclusion of suitable hydrophobic molecules. The formation of these complexes leads to significant changes of the solubility and reactivity of the guest molecules, but without any chemical modification. Thus, water insoluble molecules may become completely water solu…