2-cyanoprop-2-yl dithiobenzoate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2-cyanoprop-2-yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANS were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. H-1 NMR analysis confirmed the high chain-end functionality of the resultant polymers.

Atom transfer radical polymerization of butadiene using MoO2Cl2/PPh3 as the catalyst

Atom transfer radical polymerization has been used to successfully synthesize polybutadiene. This was achieved by using MoO2Cl2/triphenyl phosphine as the catalyst and the various organic halide compounds such as methyl-2-chloropropionate, CCl4, 1,4-dichloromethyl benzene, I-phenylethyl chloride, and benzyl chloride as initiators. The monomer conversion increased up to 50% with polymerization time. The polydispersity indices of the polymers were as high as above 1.5. However, the polymerizations were controlled and the polydispersity indices of the polymers were less than 1.5 throughout the polymerization in reverse atom transfer radical polymerization. The chemical structure of the polymer obtained was characterized by (HNMR)-H-1 and FTIR. The valency states of molybdenum in this reactive system were detected by UV-vis spectra.

Design of silicone rubber according to requirements based on the multi-objective optimization of chemical reactions

The explicit expression between composition and mechanical properties of silicone rubber was derived from the physics of polymer elasticity, the implicit expression among material composition, reaction conditions and reaction efficiency was obtained from chemical thermodynamics and kinetics, and then an implicit multi-objective optimization model was constructed. Genetic algorithm was applied to optimize material composition and reaction conditions, and the finite element method of cross-linking reaction processes was used to solve multi-objective functions, on the basis of which a new optimization methodology of crosslinking reaction processes was established. Using this methodology, rubber materials can be designed according to pre-specified requirements.

Dibenzyl trithiocarbonate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile

Reversible addition-fragmentation chain transfer polymerization has been successfully applied to polymerize acrylonitrile with dibenzyl trithiocarbonate as the chain-transfer agent. The key to success is ascribed to the improvement of the interchange frequency between dormant and active species through the reduction of the activation energy for the fragmentation of the intermediate. The influence of several experimental parameters, such as the molar ratio of the chain-transfer agent to the initiator [azobis(isobutyronitrile)], the molar ratio of the monomer to the chain-transfer agent, and the monomer concentration, on the polymerization kinetics and the molecular weight as well as the polydispersity has been investigated in detail. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and H-1 NMR analyses have confirmed the chain-end functionality of the resultant polymer.

Independence of the brittle-ductile transition from the rubber particle size for impact-modified poly(vinyl chloride)

A series of acrylic impact modifiers (AIMS) with different particle sizes ranging from 55.2 to 927.0 nm were synthesized by seeded emulsion polymerization, and the effect of the particle size on the brittle-ductile transition of impact-modified poly(vinyl chloride) (PVC) was investigated. For each AIM, a series of PVC/AIM blends with compositions of 6, 8, 10, 12, and 15 phr AIM in 100 phr PVC were prepared, and the Izod impact strengths of these blends were tested at 23 degrees C. For AIMs with particle sizes of 55.2, 59.8, 125.2, 243.2, and 341.1 nm, the blends fractured in the brittle mode when the concentration of AIM was lower than 10 phr, whereas the blends showed ductile fracture when the AIM concentration reached 10 phr. It was concluded that the brittle-ductile transition of the PVC/AIM blends was independent of the particle size in the range of 55.2-341.1 nm. When the particle size was greater than 341.1 nm, however, the brittle-ductile transition shifted to a higher AIM concentration with an increase in the particle size. Furthermore, the critical interparticle distance was found not to be the criterion of the brittle-ductile transition for the PVC/AIM blends.

Deformation mechanism of polystyrene toughened with sub-micrometer monodisperse rubber particles

Core-shell polybutadiene-graft-polystyrene (PB-g-PS) rubber particles with different ratios of polybutadiene to polystyrene were prepared by emulsion polymerization through grafting styrene onto polybutadiene latex. The weight ratio of polybutadiene to polystyrene ranged from 50/50 to 90/10. These core-shell rubber particles were then blended with polystyrene to prepare PS/PB-g-PS blends with a constant rubber content of 20 wt%. PB-g-PS particles with a lower PB/PS ratio (<= 570/30) form a homogeneous dispersion in the polystyrene matrix, and the Izod notched impact strength of these blends is higher than that of commercial high-impact polystyrene (HIPS). It is generally accepted that polystyrene can only be toughened effectively by 1-3 mu m rubber particles through a toughening mechanism of multiple crazings. However, the experimental results show that polystyrene can actually be toughened by monodisperse sub-micrometer rubber particles. Scanning electron micrographs of the fracture surface and stress-whitening zone of blends with a PB/PS ratio of 70/30 in PB-g-PS copolymer reveal a novel toughening mechanism of modified polystyrene, which may be shear yielding of the matrix, promoted by cavitation.

Pressure-dependent glass-transition temperatures of poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) blends

The pressure-dependent glass-transition temperatures (T-g's) of poly(methyl methacrylate) (PMMA)/poly(styrene-co-acrylonitrile) (SAN) blends were determined by pressure-volume-temperature (PVT) dilatometry via an isobaric cooling procedure. The Gordon-Taylor and Fox equations were used to evaluate the relationships between the T-g's and compositions of the PMMA/SAN system at different pressures. The relationships were well fitted by the Gordon-Taylor equation, and the experimental data for T-g positively deviated from the values calculated with the Fox equation. Also, the influence of the cooling rate (during the PVT measurements) on T-g was examined.

Polymerization of acrylonitrile with (diisopropylamido) bis (indenyl) lanthanides

The polymerization of acrylonitrile was studied using ( diisopropylamido) his ( indenyl) lanthanides, Ind(2)LnN(i-Pr)(2)(Ln = Y, Yb) as a single-component catalyst. The effects of the amount of catalyst, monomer concentration and polymerization temperature on catalytic activity and molecular weight of polyacrylonitrile (PAN) were studied. The results show that the catalytic activity is raised obviously with rising polymerization temperature. The monomer conversion reaches 64% under polymerization temperature, monomer concentration and catalyst concentration are 50 degreesC, 5.1 mol . L (-1) and 0. 3 % (molar ratio) sequentially. The conversion and molecular weight of the polymer increase appreciably with adding additive, PhONa. When the molar ratio of PhONa to the catalyst is three I the conversion and the molecular weight is 76% and 1.32 x 10(4), respectively. The initiation mechanism for the polymerization of acrylonitrile was proposed.

Observation of inverted phases in poly(styrene-b-butadiene-b-styrene) triblock copolymer by solvent-induced order-disorder phase transition

We report observation of inverted phases consisting of spheres and/or cylinders of the majority fraction block in a poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer by solvent-induced order-disorder phase transition (ODT). The SBS sample has a molecular weight of 140K Da and a polystyrene (PS) weight fraction of 30%. Tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were utilized to study the copolymer microstructure of a set of solution-cast SBS films dried with different solvent evaporation rates, R. The control with different R leads to kinetic frozen-in of microstructures corresponding to a different combination parameter chi (eff)Z of the drying films (where chi (eff) is the effective interaction parameter of the polymer solution in the cast film and Z the number of "blobs" of size equal to the correlation length one block copolymer chain contains), for which faster evaporation rates result in microstructures of smaller chi (eff)Z. As R was decreased from rapid evaporations (similar to0.1 mL/h), the microstructure evolved from a totally disordered one sequentially to inverted phases consisting of spheres and then cylinders of polybutadiene (PB) in a PS matrix and finally reached the equilibrium phase, namely cylinders of PS in a PB matrix. We interpret the formation of inverted phases as due to the increased relative importance of entropy as chi (eff)Z is decreased, which may dominate the energy penalty for having a bigger interfacial area between the immiscible blocks in the inverted phases.

Effects of rubber content and temperature on dynamic fracture toughness of ABS materials

The effects of rubber content and temperature on dynamic fracture toughness of ABS materials have been investigated based on the J-integral and crack opening displacement (COD, delta) concepts by an instrumented Charpy impact test. A multiple specimens R-curve method and stop block technique are used. It is shown that the materials exhibit a different toughness behavior, depending on rubber content and temperature. The resistance against stable crack initiation (J(0.2) or delta(0.2)) increases with increasing rubber content. However, J(0.2) first increased with increasing temperature until reaching the maximum value; after that, it decreases with further increasing the temperature. (C) 2000 John Wiley & Sons, Inc.

Chlorohydrin water swellable rubber compatibilized by an amphiphilic craft copolymer. I. Synthesis and characterization of compatibilizer PVA-g-PBA

The graft copolymerization of butyl acrylate onto poly(vinyl alcohol) with eerie ammonium nitrate as redox initiator in a aqueous medium has been investigated. The formation of graft copolymer was confirmed by means of IR, scanning electron microscopy (SEM), and wide-angle X-ray diffraction (WAXD). The percentage of mononer conversion and percentage of grafting varied with concentrations of initiator, nitric acid, monomer, macromolecular backbone (X-n = 1750, M = 80 000), reaction temperature and reaction time. Some inorganic salts and organic solvents have a great influence upon grafting. The reaction mechanism has been explored, and rate equations for the reaction are established. (C) 2000 John Wiley & Sons, Inc.

Polymerization of acrylonitrile with organolanthanides as single-component catalysts

Ind(2)Y(mu -Et)(2)AlEt2 and Ind(2)LnN(i-Pr)(2) (Ln = Y, Yb) were used as a single-component catalyst for the polymerization of acrylonitrile (AN) respectively. The regularity of polymerization of AN and stereoregularity of polyacrylonitrile (PAN) were also studied in both cases. Both catalysts can produce PAN with molecular weight from 10,000 to 30,000. In addition, the catalytic activity and molecular weights were increased by the addition of PhONa.