Polymerization and reaction rate studies on substituted phenylmethylbis(dimethylamino)silanes

The synthesis of seven para- or meta-substituted phenylmethylbis(dimethylamino)-silane monomers has been carried out. These silanes were polymerized with 1,4-bis(hydroxydimethylsilyl)benzene in tetrahydrofuran at 30°C, and the polymerization kinetics were followed by monitoring dimethylamine evolution for 200 min. The polymers were quenched by precipitation in methanol and molecular weight data were obtained. The polymerizations followed second-order kinetics in every case as evidenced by the linear plots of 1/(a ? x) versus time. The molecular weight data generally correlated with the specific reaction rate constant k₂ to show an increasing polymer molecular weight with increasing polymerization rate, although the range of k₂ values obtained for the substituted aminosilanes was relatively small (2.50 × 10^?5–6.67 × 10^?5 l./mole-sec). The value of k₂ increased in the following order: p-OCH₃, p-F, m-CH₃, H, m-OCH₃, p-CF₃, 3,5-di(CF₃). The logarithms of the rate constants correlated with the σ constants for the substituents, with a reaction constant, ρ of 0.391. The displacement at silicon in these reactions is discussed in terms of bimolecular mechanisms in which a four-center transition state may participate.     

Synthesis of block copolymers containing poly(ferrocenylmethyl methacrylate) units

Ferrocenylmethyl methacrylate (FMMA) has been polymerized by using LiAlH₄–tetramethyl-ethylenediamine initiation to form living polymers in high vacuum systems. The addition of methyl methacrylate or acrylonitrile to these living systems gave the block copolymers FMMA-block MMA and FMMA-block AN. The anions were not nucleophilic enough to initiate styrene polymerization. Therefore, living polystyrene was prepared (sodium naphthalide initiation in THF at ?78°C) and upon FMMA addition, styrene-block FMMA copolymers were formed. Extraction, precipitation, and gel-permeation chromatography studies were performed to examine the purity of the block copolymers.     

Cationic polymerizations of substituted 2-methylene-1,3-dioxocyclic acetals, 2-methylene-1,3-dithiolane and copolymerization of 2-methylene-1,3-dithiolane with 4-(t-butyl)-2-methylene-1,3-dioxolane1

Carbon black-supported sulfuric acid or BF₃·Et₂O-initiated polymerizations of 2-methylene-4,4,5,5-tetramethyl-1,3-dioxolane (1), 2-methylene-4-phenyl-1,3-dioxolane (2), and 2-methylene-4-isopropyl-5,5-dimethyl-1,3-dioxane (3) were performed. 1,2-Vinyl addition homopolymers of 1–3 were produced using carbon black-supported H₂SO₄ initiation at temperatures from 0°C to 60°C whereas both ring-opened and 1,2-vinyl structural units were present in the polymers using BF₃·Et₂O as an initiator. Cationic polymerizations of 2-methylene-1,3-dithiolane (4) and copolymerization of 4 with 2-methylene-4-(t-butyl)-1,3-dioxolane (5) were initiated with either carbon black-sulfuric acid or BF₃·Et₂O. Insoluble 1,2-vinyl addition homopolymers of 4 were obtained upon initiation with the supported acid or BF₃·Et₂O. A soluble copolymer of 2-methylene-1,3-dithiolane (4) and 4-(t-butyl)-2-methylene-1,3-dioxolane (5) was obtained upon BF₃·Et₂O initiation. This copolymer is composed of three structural units: a ring-opened dithioester unit, a 1,2-vinyl-polymerized 1,3-dithiolane unit, and a 1,2-vinyl polymerized 4-(t-butyl)-1,3-dioxolane unit. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2823–2840, 1999     

Ammeline–melamine–formaldehyde resins. Preparation and properties

Ammeline–melamine–formaldehyde resins (AMF Resins) containing 5–100 mol % of ammeline, were synthesized by polymerization of the preformed sodium salt of ammeline, melamine, and formaldehyde in basic medium by three methods. These resins, when cured, constitute a new class of thermosets. The rate of hydroxymethylation of the amino groups of the ammeline salt with formaldehyde was somewhat larger then that of the amino groups on melamine. At higher pH values ammeline insolubility was not a problem. The AMF resin composition was approximately equal to the mol ratio of the components originally charged. Both ammeline and melamine were consumed over the entire reaction period. Thus, it is possible to make approximately uniform random ammeline-melamine-formaldehyde resins (AMF) with any mol ratio of ammeline salt to melamine. By controlling the pH of the solution from which the resins were isolated, the (SINGLE BOND) O⁻ Na⁺/(SINGLE BOND) OH ratio could be varied. Resin melting points varied widely with the mol fraction of ammeline and the (SINGLE BOND) O⁻ Na⁺/(SINGLE BOND) OH ratio. AMF resin solubilities, shelf lives, cloud points, and water tolerance depended upon the method of preparation, pH, and other factors. The sodium salt of ammeline was hydroxymethylated in water more readily than ammeline. More highly methylolated ammeline species were readily formed in solution but upon precipitation only bis-N-hydroxymethylammeline was isolated. © 1996 John Wiley & Sons, Inc.     

Single, binary and multi-component adsorption of copper and cadmium from aqueous solutions on Kraft lignin--a biosorbent

A new biosorbent for removing toxic metal ions from water/industrial wastewater has been investigated using by-product lignin from paper production. Lignin was extracted from black liquor waste, characterized and utilized for the removal of copper and cadmium from aqueous solutions in single, binary and multi-component systems. Adsorption studies were conducted at different temperatures, lignin particle sizes, pHs and solid to liquid ratios. All the studies were conducted by a batch method to determine equilibrium and kinetic parameters. The Langmuir and Freundlich isotherm models were applied. The Langmuir model fits best the equilibrium isotherm data. The maximum lignin adsorption capacities at 25 degrees C were 87.05 mg/g (1.37 mmol/g) and 137.14 mg/g (1.22 mmol/g) for Cu(II) and Cd(II), respectively. Adsorption of Cu2+ (68.63 mg/g at 10 degrees C and 94.68 mg/g at 40 degrees C) and Cd2+ (59.58 mg/g at 10 degrees C and 175.36 mg/g at 40 degrees C) increased with an increase in temperature. Copper and cadmium adsorption followed pseudo-second order rate kinetics. From kinetic studies, various rate and thermodynamic parameters such as effective diffusion coefficients, activation energy, and activation entropy were evaluated. Adsorption occurs through a particle diffusion mechanism at temperatures 10 and 25 degrees C while at 40 degrees C it occurs through a film diffusion mechanism. The sorption capacity of black liquor lignin is higher than many other adsorbents/carbons/biosorbents utilized for the removal of Cu(II) and Cd(II) from water/wastewater in single and multi-component systems.     

Sorption of arsenic, cadmium, and lead by chars produced from fast pyrolysis of wood and bark during bio-oil production

Bio-char by-products from fast wood/bark pyrolyses, were investigated as adsorbents for the removal of the toxic metals (As(3+), Cd(2+), Pb(2+)) from water. Oak bark, pine bark, oak wood, and pine wood chars were obtained from fast pyrolysis at 400 and 450 degrees C in an auger-fed reactor and characterized. A commercial activated carbon was also investigated for comparison. Chars were sieved (>600, 600-250, 250-177, 177-149, and <149 microm) and the particle size fraction from 600 to 250 microm was used without further modification for all studies unless otherwise stated. Sorption studies were performed at different temperatures, pHs, and solid to liquid ratios in the batch mode. Maximum adsorption occurred over a pH range 3-4 for arsenic and 4-5 for lead and cadmium. Kinetic studies yielded an optimum equilibrium time of 24 h with an adsorbent dose of 10 g/L and concentration approximately 100 mg/L for lead and cadmium. Sorption isotherms studies were conducted in broad concentration ranges (1-1000 ppb for arsenic, 1x10(-5)-5x10(-3) M for lead and cadmium). Oak bark out-performed the other chars and nearly mimicked Calgon F-400 adsorption for lead and cadmium. In an aqueous lead solution with initial concentration of 4.8x10(-4) M, both oak bark and Calgon F-400 (10 g/L) removed nearly 100% of the heavy metal. Oak bark (10 g/L) also removed about 70% of arsenic and 50% of cadmium from aqueous solutions. Varying temperatures (e.g., 5, 25, and 40 degrees C) were used to determine the effect of temperatures. The equilibrium data were modeled with the help of Langmuir and Freundlich equations. Overall, the data are well fitted with both the models, with a slight advantage for Langmuir model. The oak bark char's ability to remove Pb(II) and Cd(II) is remarkable when considered in terms of the amount of metal adsorbed per unit surface area (0.5157 mg/m(2) for Pb(II) and 0.213 mg/m(2) for Cd(II) versus that of commercial activated carbon.     

BF3·OEt2-initiated polymerization of 2-methylene-1,3-dioxepanes

BF₃·OEt₂-initiated polymerizations of 2-methylene-1,3-dioxepane gave polymers composed of both ring-retained and ring-opened structures. The ring-opening content increased with an increase in polymerization temperature. Poly(4,7-dimethyl-2-methylene-1,3-dioxepane) propagated slower during BF₃·OEt₂-initiated polymerization and had a lower ring-opened content than poly(2-methylene-1,3-dioxepane). The type of acid initiator used also affected the amount of ring opening observed. Stronger acids gave less ring opening. Attempted BF₃·OEt₂-initiated copolymerizations of these seven-membered ring cyclic ketene acetals with isobutyl vinyl ether at room temperature resulted in formation of the two homopolymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 873–881, 1998     

X-ray radiation from nonlinear Thomson scattering of an intense femtosecond laser on relativistic electrons in a helium plasma

We have generated x-ray radiation from the nonlinear Thomson scattering of a 30 fs/1.5 J laser beam on plasma electrons. A collimated x-ray radiation with a broad continuous spectrum peaked at 0.15 keV with a significant tail up to 2 keV has been observed. These characteristics are found to depend strongly on the laser strength parameter a(0). This radiative process is dominant for a(0) greater than unity at which point the relativistic scattering of the laser light originates from MeV energy electrons inside the plasma.