Hot-drawing of poly(methyl methacrylate) and simulation using a glass-rubber constitutive model

The large-deformation three-dimensional glass-rubber constitutive model for isotropic, amorphous, linear polymers near the glass transition, previously proposed, has been extended to include a spectrum of network relaxations. In addition, an experimental programme of uniaxial tension and compression tests was carried out on high molecular weight cast sheets of poly(methyl methacrylate) (PMMA), with varying strain-rate and temperature across the range from 114 to 190 °C, encompassing the thermoforming range of practical importance. The extended model was found to fit successfully the data for PMMA, provided a doublet network relaxation spectrum was employed. The original model, with only a single network relaxation, was found to be grossly inadequate when there was significant network relaxation by entanglement slippage. Parameters of the model for PMMA, obtained by fitting to the new data, were compared with values obtained by other routes.     

Preparation of fatty acid methyl esters for gas-chromatographic analysis of lipids in biological materials

Theoretically, preparation of fatty acid methyl esters (FAMEs) deals with reversible chemical reactions in a complex system. Methodologically, there are numerous ways, generally characterized by the type of catalysts used and steps involved. Although there are more than a half dozen common catalysts, the majority fall into either acidic (HCl, H₂SO₄ and BF₃) or alkaline types (NaOCH₃, KOH and NaOH), with each having its own catalytic capability and application limitations. In terms of steps, many conventional methods, including those officially recognized, consist of drying, digestion, extraction, purification, alkaline hydrolysis, transmethylation/methylation and postreaction work-up. Although these methods are capable of providing reliable estimates if some precautions are taken, they are cumbersome, time-consuming and cost-inefficient. A new approach has been to transmethylate lipidsin situ. Due to its simplicity, high sensitivity, comparable reliability and capability to determine total fatty acids, the method of direct transmethylation is finding a unique place in lipid determination. Regardless of which method is used, quantitative methylation requires chemists to take precautions at every step involved, particularly during FAME formation and subsequent recovery steps. Evidently, there is an urgent need for more systematic studies, guided by the chemical principle of reactions involved and physicochemical properties of regents and end products, into factors affecting these steps. Hopefully, this will lead to an improved method, which measures lipid composition in biological materials not only with high accuracy but also with high efficiency and minimum costs.     

Cover Picture: Toward Large‐Scale Alignment of Electrohydrodynamic Patterning of Thin Polymer Films (Adv. Funct. Mater. 15/2006)

By integrating lithography and self‐assembly via electrohydrodynamic instabilities, Russel and co‐workers are able to guide initially flat polymer films to evolve into periodic arrays of pillars over regions much greater in extent than their natural domain sizes, as detailed on p. 1992. Novel structures that involve a combination of linear ridges and pillars are also produced, mainly as as result of the dynamic merging among preformed pillars. To pattern thin polymer films via electrohydrodynamic instabilities, we design and utilize two different kinds of mask patterns to guide pillars into alignment over regions much greater in extent than their natural domain sizes. First, narrow protruding ridges that intersect to form regular patterns on the mask trigger the growth of pillars beneath. Later, square and triangular packings of pillars develop in the regions enclosed by those ridges, preserving the registry from one domain to the next over a much larger area than within individual domains in unpatterned portions of the mask. Second, small square protrusions that are prealigned into a large regular array on the mask guide the formation of square packings of pillars in domains that conform to the mask, forming a large array of pillars. Novel structures involving a combination of linear ridges and pillars are also produced mainly due to the dynamic merging among preformed pillars. Finally, we find vertex symmetry of the mask pattern is necessary for generating and preserving ordered patterns on the polymer film.     

Synthesis and characterisation of N-toluyl methacrylatoethyl carbamates,homopolymers and copolymers with methyl methacrylate

The paper describes the synthesis of N-2/4-toluyl methacrylatoethyl carbamates using 2/4-toluyl isocyanate and 2-hydroxyethyl methacrylate. Homopolymerisation and copolymerisation of these novel monomers with methyl methacrylate was carried out using benzoyl peroxide as an initiator and tetrahydrofuran as solvent. Photopolymerisation of N-4-toluyl methacrylatoethyl carbamate could be carried out without the use of photosensitiser. Structural characterisation of copolymers was done using ¹H-NMR. Thermal stability of copolymers was evaluated in a nitrogen atmosphere by dynamic thermogravimetry.     

Cationic ring-opening polymerization of hexamethylcyclodisilazane: General aspects and tentative mechanisms

The ring-opening polymerization of hexamethylcyclodisilazane (D_2NMe), initiated by methyl triflate in 1,2-dichloroethane, forms in the first, fast kinetic step both linear polymer and cyclic dimer (D_4NMe). Subsequently a slow depolymerization process occurs leading to exclusively cyclotrisilazane (D_3NMe). On the basis of kinetic measurements carried out using an adiabatic calorimetric technique and complementary experiments, mechanisms of both propagation, cyclization and back-biting reactions are proposed. The influence of the reaction temperature was also studied; it is demonstrated that, at low temperature, polymerization does not lead to cyclic oligomer formation. In such conditions, the polymerization presents a ‘living’ character.     

纳米镓/聚甲基丙烯酸甲酯复合材料的原位超声合成与表征

超声作用于低熔点金属镓,使其超细化为纳米级的镓粒子,并采用无引发剂的乳液聚合方法制备出GA/聚甲基丙烯酸甲酯(PMMA)纳米复合粒子,并分析了其微观结构。结果表明纳米镓的形态和结构因有无表面改性剂而不同;乳液聚合得到的纳米镓复合粒子是核壳结构型,粒子大小为50~80 NM,内核金属镓粒径为30~50 NM,与聚合物存在一定的化学作用。     

Preparation and properties of silicone‐containing poly(methyl methacrylate) gels

Poly(methyl methacrylate) (PMMA) gels with varying amounts of silicone and solvent and constant amounts of crosslinker were prepared by solution free radical crosslinking copolymerization of methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDM), tetraethoxysilane (TEOS) and vinyltriethoxysilane (VTES) comonomer systems. They were then studied in benzene at a total monomer concentration of 3.5 mol L^?1 and 70 °C. The conversion of monomer, volume swelling ratio, weight fraction and gel point were measured as a function of the reaction time, silicone concentration and benzene content up to the onset of macrogelation. Structural characteristics of the gels were examined by using equilibrium swelling in benzene, gel fraction and Fourier‐transform infrared (FTIR) analysis. The morphology of the copolymers was also investigated by SEM. Based on the obtained results, it was concluded that the FTIR data did not have the capacity to show the presence of the VTES or TEOS moiety in these kinds of copolymers. On the other hand, the variation of weight fraction of gel, W_g, and its equilibrium volume swelling ratio in benzene, q_v, exhibited the same behaviour as that of MMA/EGDM copolymers. Also, the dilution of the monomer mixture resulted in an increase in the gel point and swelling degree and a decrease in the percent of conversion and gel fraction. Finally, TEOS is not an ideal silicone compound for reaction in the MMA/EGDM copolymerization system, whereas VTES is a suitable silicone comonomer for this system and it has been proved useful. Copyright © 2005 Society of Chemical Industry     

Effect of temperature on methyl radical generation over Sr/La2O3 catalysts

The role of gas phase CH₃ radicals in the oxidative coupling of CH₄ over 1 wt% Sr/La₂O₃ is supported by the observations that (i) this is a very effective catalyst for the generation of CH₃ · radicals and (ii) the concentration of CH₃ · radicals increases with temperature over the range of 450 °C–800 °C.     

模块化蓝光光存储性能静态测试系统

蓝光光存储是信息存储领域发展的一个重要方向。测试系统是研究蓝光光存储材料的必备条件，为建立蓝光光存储研究平台，设计和搭建了一套模块化蓝光光存储性能静态测试系统。激光工作波长为406．7nm。系统采用调制解调技术降低系统噪声，提高测量粘度：采用光点移动模式降低对样品尺寸的要求；采用纳米平台提高记录点的反复定位性能。实验结果证明测试系统性能良好，可以满足蓝光光存储性能静态测试要求。