High char‐yielding poly[acrylonitrile‐co‐(itaconic acid)‐co‐(methyl acrylate)]: synthesis and properties

Polyacrylonitrile terpolymers of various compositions consisting of acrylonitrile (AN), itaconic acid (IA) and methyl acrylate (MA) were synthesized by solution polymerization in dimethylsulfoxide. Increase in concentration of either IA or MA retarded the overall polymerization rate and the polymer molecular weight. The system consisting of AN + MA and varying IA concentration was more prone to retardation in comparison with the system composed of AN + IA with variable MA concentration. The retardation factors were quantified. Minor quantities of MA boost the reactivity of IA in the terpolymer system. The terpolymer was richer in MA vis‐à‐vis the feed. The thermal characteristics of the terpolymer were examined as a function of its composition. In contrast to the copolymer of AN and IA requiring 1–1.5 mol% IA, the terpolymer required an IA content of approximately 2.5 mol% for optimum thermal stability. The polymer with 90 mol% AN, 2.5 mol% IA and 7.5 mol% MA exhibited reasonably good char‐forming characteristics and thermal stability. The overall crystallinity and crystallite size of the polymers were found to decrease on incorporation of the comonomers. The ‘aromatization index’ of the copolymer increased with the temperature of pyrolysis through re‐organization of the tetrahydropyridine ladder structure. Copyright © 2005 Society of Chemical Industry     

Preparation of flexible polyhedral particles via concentrated emulsion templating polymerization

This paper presents recent efforts on the preparation of flexible polyhedral particles via concentrated emulsion templating polymerization in which the hydrophilic monomer (acrylamide) and hydrophobic monomer (butyl acrylate) are polymerized simultaneously in the continuous and dispersed phase, respectively. Such templating polymerization has been enhanced in our systems owing to the introduction of acrylamide monomer and their higher polymerization rate in continuous phase as compared with butyl acrylate in dispersed phase. Diffusion between the different phases was also inhibited. Furthermore, the stability of the concentrated emulsion and the molecular weight of the produced poly(butyl acrylate) were found to be significantly affected by the amount of redox initiator. The morphology of the particles could be controlled by varying the volume fraction of the dispersed phase and the polyhedral particles were achieved at higher volume fraction. Copyright © 2005 Society of Chemical Industry     

Optimization by random search with jumps

We give a random optimization (RO) algorithm to optimize a real‐valued function of n real variables. During the optimization process, interpolation points are examined to follow valleys, and jumps to new starting points are executed to avoid numerous iterations in local minima. Convergence with probability one to the global minimum of a function is proved. The proposed RO method is a simple, derivative‐free and computationally moderate algorithm, with excellent performance compared to other RO methods. Seven functions, which are commonly used to test the performance of optimization methods, are used to evaluate the performance of the RO algorithm given here. Copyright © 2004 John Wiley & Sons, Ltd.     

Preparation of ultra‐low‐density microcellular materials

Microcellular polymeric materials can be obtained by the polymerization of a high‐internal‐phase emulsion. These materials are good candidates as targets toward inertial confinement fusion. This application requires severe specifications, including a very low density and a small cell size. In this study, we examined the influence of parameters such as emulsification conditions, surfactant nature, and the presence of a porogen on the obtainment of those requirements. It was possible to obtain microcellular polymeric foams with apparent densities as low as 0.0126 g/cm³. However, it was difficult to obtain very low material density and still maintain a small average pore size. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2053–2063, 2005     

Nanostructured polymer blends: Synthesis and structure

Nanostructured polymer blends prepared via anionic ring opening polymerizations of cyclic monomers in the presence of a pre-made polymer melt exhibit a number of special properties over traditional polymer blends and homopolymers. Here, we report on a simple and versatile method of in situ polymerization of macrocyclic carbonates in the presence of a maleic anhydride polypropylene (mPP) matrix and a surface-active compatibilizer (i.e. PC grafted onto a mPP backbone generated in situ) to yield a micro- and nanostructured polymer blends consisting of a polycarbonate (PC) minor phase, and a polypropylene (PP) major phase. By varying the processing conditions and concentration of the macrocyclic carbonate it was possible to reduce the size of the PC dispersions to an average minor diameter of 150 nm. NMR and TEM characterizations indicate that the PC dispersions do not influence crystal content in the PP phase. Overall, the results point to a simple strategy and versatile route to new polymeric materials with enhanced benefits.     

Identification of photoluminescence features of an epoxy resin based on components features and curing effects

Photoluminescence features in a commercial grade cured DGEBA-based epoxy resin have been investigated with as objective to determine which of the material compounds are responsible for cured resin emissions. The origin of the bands has been approached by considering photoluminescence of base resin and hardener taken separately, of their mixture, and in the course of curing. Most of the bands observed in the cured resin could be interpreted based on those found in the components taken separately. Fluorescence of the cured resin appears dominated by two broad bands that are characteristic of the hardener and exhibits a blue shift by up to 30 nm in the course of curing which could be used for cure monitoring purpose of the investigated system. Fluorescence of the base resin is clearly detected in the resin cured with tertiary amine as catalyser. However, it is very weak if the catalyser is not added. Two phosphorescence processes have been isolated in the cured resin, one of them being related to the base resin. Finally, a chemiluminescence spectrum has been recorded in the course of curing, which has been related to either curing-related reactions or to an oxidation process.     

粘土矿物用于乙烯聚合催化剂的研究 Ⅰ.以凹凸棒石粘土为载体的乙烯聚合催化剂

研究了以凹凸棒石粘土为载体,负载TiCl4制备的乙烯聚合催化剂的结构、性能及制备规律。结果表明,催化剂中Ti的负载量随焙烧温度的提高而逐渐降低,聚合活性随焙烧温度的提高呈上升趋势,但过高的焙烧温度也会导致粘土晶体结构的彻底破坏而不利于活化粘土活性的提高;通过采用烷基铝等有机金属化合物处理粘土同样可以极大地改善粘土性质,提高催化活性。不同助催化剂对以凹凸棒石粘土为载体的催化剂的聚合性能有较大影响。     

Synthesis and characterization of functional gradient copolymers of glycidyl methacrylate and butyl acrylate

Epoxy-functional spontaneous gradient copolymers of glycidyl methacrylate (G) and n-butyl acrylate (B) were synthesized via atom transfer radical polymerization (ATRP). The copolymerization reactions were carried out in toluene solution at 70 °C, using methyl 2-bromopropionate (MBrP) as initiator and copper chloride with N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The kinetic behaviour of the statistical copolymerizations was studied in a wide composition interval with molar fractions of G ranging from 0.10 to 0.75. The synthesized copolymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. ¹H NMR was employed to determine the copolymer composition, demonstrating the gradient character of the copolymers along the main chain in the whole monomer conversion interval. Apart from this, the sequence distribution and stereoregularity were analyzed. These microstructural experimental data agreed well with those calculated from Mayo-Lewis terminal model (MLTM) and a Bernoullian statistic with an isotacticity parameter of σ_G = 0.28 and a coisotacticity parameter of σ = 0.30.     

Synthesis and physicochemical characterization of a well-defined poly(butadiene 1,3)-block-poly(dimethylsiloxane) copolymer

For the first time, order-order and order-disorder transitions were detected and characterized in a model diblock copolymer of poly(butadiene-1,3) and poly(dimethylsiloxane) (PB-b-PDMS). This model PB-b-PDMS copolymer was synthesized by the sequential anionic polymerization (high vacuum techniques) of butadiene 1,3 (B) and hexamethylciclotrisiloxane (D₃), and subsequently characterized by nuclear magnetic resonance (¹H and ¹³C NMR), size exclusion chromatography (SEC), Fourier Transform infrared spectroscopy (FTIR), Small-Angle X-ray scattering (SAXS) and rheology. SAXS combined with rheological experiments shows that the order-order and order-disorder transitions are thermoreversible. This fact indicates that the copolymer has sufficient mobility at the timescale and at the temperatures of interest to reach their equilibrium morphologies.