Cationic polymerization of styrene in a neutral ionic liquid

The cationic polymerization of styrene in a neutral ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate, with a 1‐phenetyl chloride/TiCl₄ initiating system is reported. The polymerization proceeds to a high conversion, but an analysis of the matrix‐assisted laser desorption/ionization time‐of‐flight spectra of the polymers indicates that chain transfer is significant, leading to a lack of control over the molecular weight and molecular weight distribution. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3230–3235, 2004     

Dark cure studies of cationic photopolymerizations of epoxides: Characterization of kinetic rate constants at high conversions

The effective propagation rate constant (k_p; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the k_p as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the k_p values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004     

Tetrafunctional initiators for cationic polymerization of olefins

3,3′,5,5′‐Tetrakis(2‐chloro‐2‐propyl)biphenyl (biphenyl tetracumyl chloride, BPTCC) and 1,3‐bis[3,5‐bis(2‐chloro‐2‐propyl)phenoxy]propane (diphenoxypropane tetracumyl chloride, DPPTCC) were synthesized as initiators for quasiliving cationic polymerization of isobutylene (IB). In the synthesis of BPTCC, tetrafunctionality was achieved via the coupling of dimethyl 5‐bromoisophthalate (DMBI) using nickel dibromide bis(triphenylphosphine) and zinc in the presence of a base; in the synthesis of DPPTCC, two equivalents of dimethyl 5‐hydroxyisophthalate were linked via reaction with 1,3‐dibromopropane in the presence of potassium carbonate. Both initiators were used to initiate the polymerization of IB under quasiliving cationic polymerization conditions. PIB initiated from BPTCC revealed a chain end/molecule value (as determined by ¹H‐NMR) of 3.85, verifying the nearly exclusive production of 4‐arm polyisobutylene (PIB). GPC analysis revealed a narrow peak representing the target four‐arm PIB, with a slight shoulder at high elution volumes (low molecular weights). GPC analysis of the PIB initiated by DPPTCC revealed multimodal distributions, suggesting the formation of two‐, three‐, and four‐arm star polymers during the polymerization. This behavior was attributed to Friedel–Crafts alkylation of the initiator core after the addition of one IB unit, which was activated by the electron‐donating oxytrimethyleneoxy linking moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5942–5953, 2004     

Composite Silica Particles Using a Mixture of Organosilane Monomers

Composite silica particles were synthesized by a two-step (acid-base) process in an aqueous solution with a mixture of organoalkoxysilane monomers. The two-step process separates the hydrolysis and condensation procedures to easily control condensation rate. In this study, the silane monomers used were phenyltrimethoxysilane (PTMS), vinyltrimethoxysilane (VTMS), methyltrimethoxysilane (MTMS), and tetraethyl-orthosilicate (TEOS). The physical properties of the resultant composite particles were investigated with the change in the molar ratio of monomers. The size of the particles increased with increasing the molar ratio of R_aSi(OR)₃/R_bSi(OR)₃ or R_aSi(OR)₃/TEOS (R_a: phenyl; R_b: vinyl, methyl).     

Comparative behavior of polybutadiene and polynorbornene‐based latices prepared by dispersion ring‐opening metathesis polymerization with a poly(ethylene oxide) macromonomer

This study critically examines the similarities and differences between poly(ethylene oxide) (PEO) stabilized latices of polynorbornene and polybutadiene. Features such as the kinetics of copolymerization of norbornene and cyclooctadiene with a macromonomer of PEO, the particles' size and morphology, the type of copolymer formed, and the stability of these latices were investigated and the results obtained are considered. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2705–2716, 2004     

Synthesis of Cationic PEM Emulsion and Application in Waste Water Treatment

Cationic polymer as a kind of flocculant is widely applied in purification treatment of waste water. Because it has positive charge group, it is able to connect strongly the suspended matters, short cellulose and other microparticles. The research on synthesis of cationic polymer and application in treatment of waste water is very universal abroad. But domestic research on those is not general. The technology of synthesis of PEM is simple, and the production cost is low. It is easy to apply in treatment of waste water.Synthesis of PEM Emulsion FlocculantSome distilled water, PVA(poly(vinyl alcohol)), EA(ethyl acrylate), and K2S2O8(potassium persulfate) were put into reaction vessel. Kept stirring up under nitrogen. When heated the solution to 40℃, dropped the water solution of MTA[(2-methacryloxylethyl)trimethyl ammonium].Maintained the temperature at 70℃, reacted about 7-8 hours. Then got the PEM emulsion. Changed the ratio of EA and MTA. Obtained a series of PEM emulsions.Stability and Convertibility of PEM EmulsionThe test results showed that when the EA/MTA was 85/15, the PEM emulsion was most stable.When the total monomer quantity was 35%, the convertibility of PEM emulsion was the highest,i.e.98.6%.The MTA Copolymerization Ratio and Morphology of PEM EmulsionWhen the monomers EA/MTA=85/15 and total monomer quantity was 35%, the MTA copolymerization ratio of PEM emulsion was 95.15%(the highest), and the PEM emulsion was some microspheres with 100-180nm of diameter.The Test Results of PEM Emulsion in Treatment of Waste Water The PEM emulsion flocculant was applied in treatment of waste water of paper mill, and measured the precipitation time(t) and transmittancy(T). The test results were showed in table 1. The optimum value of PEM which was able to make the waste water of paper mill into clear water was 0.008%.     

Hybrid free radical/cationic frontal photopolymerizations

The irradiation of hybrid photopolymer systems consisting of a free radically polymerizable multifunctional acrylate monomer and a cationically polymerizable epoxide or oxetane monomer was conducted under conditions where only the free radical polymerization takes place. This results in the formation of a free‐standing polyacrylate network film containing quiescent oxonium ions along with the unreacted cyclic ether monomer. The subsequent application of a point source of heat to the film ignites a cationic ring‐opening frontal polymerization that emanates from that site and propagates to all portions of the irradiated sample. This article examines the impact of various molecular structural and experimental parameters on these novel hybrid frontal polymerizations that produce interpenetrating network polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4331–4340, 2007     

Curcumin: A naturally occurring long‐wavelength photosensitizer for diaryliodonium salts

Curcumin, a naturally occurring, intensely yellow dye extracted from the spice turmeric, is an efficient photosensitizer for diaryliodonium salt photoinitiators at wavelengths ranging from 340 to 535 nm. With curcumin as a photosensitizer, it is possible to carry out the cationic photopolymerization of a wide variety of epoxide, oxetane, and vinyl monomers with long‐wavelength UV and visible light. An example of the photopolymerization of an epoxide monomer with ambient solar irradiation is provided. Several other curcumin analogues were synthesized, and their use as photosensitizers is examined. With such photosensitizers, the range of spectral sensitivity can be extended well into the visible region of the electromagnetic spectrum. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5217–5231, 2005     

Photoinitiated curing of mono‐ and bifunctional epoxides by combination of active chain end and activated monomer cationic polymerization methods

Photoinitiated cationic polymerization of mono‐ and bifunctional epoxy monomers, namely cyclohexeneoxide (CHO), 4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexanecarboxylate (EEC), respectively by using sulphonium salts in the presence of hydroxylbutyl vinyl ether (HBVE) was studied. The real‐time FTIR spectroscopic, gel content determination, and thermal characterization studies revealed that both hydroxyl and vinyl ether functionalities of HBVE take part in the polymerization. During the polymerization, HBVE has the ability to react via both active chain end (ACE) and activated monomer mechanisms through its hydroxyl and vinyl ether functionalities, respectively. Thus, more efficient curing was observed with the addition of HBVE into EEC‐containing formulations. It was also demonstrated that HBVE is effective in facilitating the photoinduced crosslinking of monofunctional epoxy monomer, CHO in the absence of a conventional crosslinker. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4914–4920, 2007     

Intermittency in the Slow Particle Emission During Hadron–Nucleus Interactions

The study of the angular distribution of slow particles during high energy hadron-nucleus interaction indicates that emission of slow particles takes place from a thermally non-equilibrated system. This evidence has come out from the presence of intermittency - a phenomenon that reveals a fractal structure and represents a self-similarity in the particle production process. Hence, this study highlights inadequacy of cascade-evaporation model and advocates the need of its refinement.