Effect of graft chain length of the stabilizer on dispersion polymerization of methyl methacrylate in petrol

To carry out dispersion polymerization of methyl methacrylate (MMA) in petrol, we have used a poly(MMA) grafted-poly(12-hydroxystearic acid) copolymer as the stabilizer. This special copolymer was prepared as a solution in a mixture of ethyl acetate and butyl acetate solvents. We investigated the effect of graft chain length of the stabilizer on the dispersion polymerization in petrol. We synthesized the stabilizer copolymer with n = 1–4 and determined the rate and the molecular weight of the PMMA formed. There is no dispersion polymerization for n = 1. However, for any other n, for a given stabilizer concentration, as the chain length of the graft is increased, the molecular weight as well as the rate of PMMA formation increases. As opposed to this for a given graft length as the concentration of the stabilizer increases, the molecular weight of PMMA first rises, but for a larger concentration, it begins to fall after undergoing a maximum. In this work, we modeled the heterogeneity of the reaction mass and proposed a mathematical model for dispersion polymerization of MMA in petrol. The computer results are found to conform to the experimentally observed molecular weight of the PMMA. © 1993 John Wiley & Sons, Inc.     

Electroless Plating of Copper on Fluorinated Polyimide Films Modified by Plasma Graft Copolymerization and UV‐induced Graft Copolymerization with 4‐Vinylpyridine

Surface modification of two types of fluorinated polyimide (FPI) films, either by plasma polymerization and deposition of 4‐vinylpyridine (4VP) or by UV‐induced graft copolymerization with 4VP under atmospheric conditions, was carried out for adhesion enhancement with the electrolessly deposited copper. X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) results revealed that the pyridine groups in the plasma polymerized 4VP (pp‐4VP) layer could be preserved to a large extent under proper glow discharge conditions. The grafted 4VP layer with well‐preserved pyridine groups was used not only as the chemisorption sites for the palladium complexes (without the need for prior sensitization by SnCl₂) during the electroless plating of copper, but also as an adhesion promotion layer for the electrolessly deposited copper. The T‐peel adhesion strength of the electrolessly deposited copper with both the 4VP plasma‐polymerized FPI (pp‐4VP‐FPI) film and the 4VP graft‐copolymerized FPI (4VP‐g‐FPI) film was much higher than that of the electrolessly deposited copper with the pristine or the Ar plasma‐treated FPI films. The high adhesion strength between the electrolessly deposited copper and the surface‐modified FPI film was attributed to the fact that the plasma‐polymerized and the UV graft‐copolymerized 4VP chains were covalently tethered on the FPI surfaces, as well as the fact that these grafted 4VP polymer chains were spatially and reactively distributed into the copper matrix.

     

Effect of flow rate and temperature on crystallization kinetics,crystallinity index,and elastic modulus of PEEK

Dynamic, in situ wide angle X-ray scattering (WAXS) studies of the melt crystallization of injection-molded poly(ether ether ketone) (PEEK) have been carried out using an X-ray diffractometer and a position-sensitive detector. A test cell has been fabricated to fit inside the diffractometer and yet work as a complete injection molding apparatus. The rate of crystallization has been shown to increase with decreasing crystallization temperature and/or increasing flow rate in the mold. The crystallization rate decreases dramatically with increase in melt soak time at 400°C. The crystallinity index, which affects the stiffness, toughness, and fracture behavior of PEEK, has been measured under various processing conditions, by wide angle X-ray scattering, so as to optimize the process parameters: molding time, mold temperature, melt temperature, soak time at melt temperature, and flow rate. It has been shown that the crystallinity and hence the elastic modulus increase with increase in crystallization temperature and/or flow rate. Chain orientation has been shown to be absent in the bulk of the injection-molded specimens under normal molding conditions.     

Sequence analysis and fiber properties of a blend of poly(ethylene terephthalate) and poly(ethylene terephthalate‐co‐4,4′‐bibenzoate)

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐4,4′‐ bibenzoate) (PETBB) are prepared by coextrusion. Analysis by ¹³C‐NMR spectroscopy shows that little transesterification occurs during the blending process. Additional heat treatment of the blend leads to more transesterification and a corresponding increase in the degree of randomness, R. Analysis by differential scanning calorimetry shows that the as‐extruded blend is semicrystalline, unlike PETBB15, a random copolymer with the same composition as the non‐ random blend. Additional heat treatment of the blend leads to a decrease in the melting point, T_m, and an increase in glass transition temperature, T_g. The T_m and T_g of the blend reach minimum and maximum values, respectively, after 15 min at 270°C, at which point the blend has not been fully randomized. The blend has a lower crystallization rate than PET and PETBB55 (a copolymer containing 55 mol % bibenzoate). The PET/PETBB55 (70/30 w/w) blend shows a secondary endothermic peak at 15°C above an isothermal crystallization temperature. The secondary peak was confirmed to be the melting of small and/or imperfect crystals resulting from secondary crystallization. The blend exhibits the crystal structure of PET. Tensile properties of the fibers prepared from the blend are comparable to those of PET fiber, whereas PETBB55 fibers display higher performance. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1793–1803, 2004     

Microstructure determination and thermal studies of n‐acryloylcarbazole/vinyl acetate copolymers

Copolymers of N‐acryloylcarbazole (A) and vinyl acetate (V) were synthesized by bulk polymerization using benzoyl peroxide (BPO) as free‐radical initiator at 65°C in different in‐feed ratios. The composition of the copolymer was determined by ¹H‐NMR spectrum. The comonomer reactivity ratios, determined by Kelen–Tudos (KT) and nonlinear error‐in‐variables (EVM) methods, were r_A= 16.75 ± 1.38, r_V = 0.015 ± 0.002, and r_A = 16.36, r_V = 0.015, respectively. Complete spectral assignments of the ¹H and ¹³C{¹H} NMR spectra of the copolymers were done by the help of distortionless enhancement by polarization transfer (DEPT) and two‐dimensional NMR techniques such as heteronuclear single quantum coherence (HSQC) and total correlation spectroscopy (TOCSY). The methine and methylene carbon resonances were found to be compositional as well as configurational sensitive. The signals obtained were broad pertaining to the restricted rotation of bulky carbazole group. The thermal stability and glass‐transition temperatures (T_g) of the copolymers were found to be dependant on polymer composition and characteristic of rotational rigidity of the polymer chain. Variation in the values of T_g with the copolymer composition was found to be in good agreement with theoretical values obtained from Johnston and Barton equations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2720–2733, 2007     

Lyso platelet activating factor (LysoPAF) and its enantiomer. Total synthesis and carbon-13 NMR spectroscopy

Described is a reaction sequence for the total synthesis of lyso platelet activating factor (lysoPAF; 1-O-alkyl-sn-glycero-3-phosphocholine) and its enantiomer. The procedure is versatile and yields optically pure isomers of defined chain length. The synthesis is equally suited for the preparation of lysoPAF analogues and its enantiomers with unsaturation in the long aliphatic chain. First,rac-1(3)-O-alkylglycerol is prepared by alkylation ofrac-isopropylideneglycerol with alkyl methanesulfonate followed by acid-catalyzed removal of the ketal group. The primary hydroxy group of alkylglycerol is then protected by tritylation, the secondary hydroxy group is acylated, and the protective trityl group is removed under mild acidic conditions with boric acid on silicic acid, essentially without acyl migration. Condensation of the diradylglycerol with bromoethyl dichlorophosphate in diethyl ether, hydrolysis of the resulting chloride, and nucleophilic displacement of the bromine with trimethylamine givesrac-1-O-alkyl-2-acylglycero-3-phosphocholine in good overall yield. The racemic alkylacylglycerophosphocholine is finally treated with snake venom phospholipase A₂ (Ophiophagus hannah) which affords 1-O-alkyl-sn-glycero-3-phosphocholine (lysoPAF) of natural configuration in optically pure form. The “unnatural” 3-O-alkyl-2-O-acyl-sn-glycerol-1-phosphocholine enantiomer, which is not susceptible to phospholipase A₂ cleavage, gives 3-O-alkyl-sn-glycero-1-phosphocholine upon deacylation with methanolic sodium hydroxide. Homogeneity and structure of the intermediates and final products were ascertained by carbon-13 nuclear magnetic resonance spectroscopy on monomeric solutions.     

Thermal gas effusion from diamond-like carbon films

Good-quality diamond-like carbon films (6 at.% H₂, 2400 kgf/mm² microhardness, 2.7 eV bandgap, higly insulating) have been obtained by the DC glow discharge decomposition of acetylene. Mass spectroscopic thermal effusion measurements were carried out on the films deposited under different deposition conditions. Analyses of hydrogen in conjunction with hydrocarbon effusing species yield information on the microstructure and nature of C---H bonding configurations. It is shown to be a useful analytical tool to study hydrogenated amorphous carbon films of different microstructures varying from polymer-like to diamond-like.     

Study of the influence of reaction conditions on the degree of substitution,intrinsic viscosity,and yield of oxidized cellulose acetate by factorial experimental design

A half‐fraction, two‐level, four‐factor factorial experimental design was used to study the effects of the acetic anhydride concentration, reaction temperature, reaction time, and sulfuric acid concentration on the degree of substitution, intrinsic viscosity, and yield of oxidized cellulose acetate (OCA). Oxidized cellulose containing 20% (w/w) carboxylic acid was used as the starting material. The data were fitted by multiple regression analysis with SAS software. The correlation coefficients obtained from plots of the predicted and observed values for the degree of substitution, intrinsic viscosity, and yield were 0.985, 0.993, and 0.991, respectively. Residual normal plots of the regression models showed a linear relationship. Lenth and main‐factor‐effect plots revealed an increase in the degree of substitution of OCA with an increasing concentration of acetic anhydride. The latter had no effect on the intrinsic viscosity and yield of OCA. An increase in the reaction temperature led to an increase in the degree of substitution and a decrease in the intrinsic viscosity and yield of OCA. The influence of the reaction time on the degree of substitution and intrinsic viscosity followed a trend similar to that observed with the reaction temperature, but the yield of OCA was unaffected. Increasing the concentration of sulfuric acid reduced the degree of substitution, intrinsic viscosity, and yield of OCA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 696–705, 2005     

A class of discontinuous dynamical systems IV. A laboratory air-water system

An air-water experimental system consisting of two inlets and one outlet is constructed and characterised. It reaches the state of sliding mode, or equivalently, two phase slug flow. The linear hydraulic model proposed in the literature is adequate to describe it. Experimental data are used to tune this model. The resistance to the flow of air through the outlet valve during the two phase flow is much larger than that when air alone flows out. At the operating range, the resistance to water flow is not affected by the presence of air.