Challenges in the Emulsion Co- and Terpolymerization of Vinylidene Fluoride.

The feasibility of co- and terpolymerizing vinylidene fluoride (VDF) with ethylene (C2) and/or vinyl acetate in an emulsion polymerization process was studied for different C2 pressures, initiator concentration, surfactant concentration, pH, C2 injection protocols, and the influence of vinyl acetate (VAc) in the reaction medium. Pressure drop and temperature profiles as well as gravimetry were used to follow the rate of polymerization. The microstructure of the synthesized products was assessed by fluorine and hydrogen nuclear magnetic resonance spectroscopy (19F and 1H NMR). C2 was found to cause an inhibition/retardation effect on the copolymerization with VDF (and with VDF/VAc). However, statistical copolymers containing VAc and VDF were synthesized by reducing as much as possible the homogeneous nucleation of the VAc in the water phase. This was done by adding VAc into the reaction after the homogeneous-coagulative nucleation of VDF takes place (around 5 min after initiator injection).

Styrene-Butadiene Rubber by Miniemulsion Polymerization Using In Situ Generated Surfactant.

An alternative approach for the synthesis of styrene butadiene rubber (SBR) copolymer latexes was explored in order to obtain low gel fractions and high solid contents. The ultra-turrax-assisted miniemulsion stabilized by in situ surfactant generation was adopted as the main strategy since this technique can inhibit the eventual presence of secondary nucleation producing polybutadiene particles and also control the cross-linking degree. Styrene monomer was first miniemulsified using an ultra-turrax and in situ generated surfactant using either hexadecane (HD) or octadecyl acrylate (ODA) as the hydrophobe. Dynamic light scattering (DLS) measurements of droplet size indicated faster stabilization and the production of smaller droplet diameters ca. 190 nm (PdI = 0.08) when employing in situ generated potassium oleate (K-Oleate) in comparison to SDS-based miniemulsions. High butadiene-level SBR latexes with ca. 50% solids content, a glass transition temperature (Tg) of -52 °C, and a butadiene to styrene weight ratio of 75:25, were then obtained using the miniemulsion droplets as seeds. Turbiscan and DLS measurements revealed a very stable resulting latex with SBR particle diameter of ca. 220 nm and a low polydispersity index (PdI). Secondary nucleation was prevented as indicated by the low Np/Nd value. Cryo-TEM images showed a narrow distribution of particle size as well as the absence of agglomeration. The gel content was below 10% when tert-dodecyl mercaptan (t-DM) was used as chain transfer agent (CTA).

Site count: is a high-pressure quenched-flow reactor suitable for kinetic studies of molecular catalysts in ethylene polymerization?

Understanding the kinetics of olefin polymerization with Ziegler-Natta and related catalysts means identifying the main kinetic parameters such as k(p) and concentration of active sites. The high-pressure quenched-flow technique could be an absolute method for counting active sites and for activation studies of molecular catalysts. A kinetic study of metallocene catalysts and a phenoxy-imine titanium catalyst in the first instants of polymerization is presented in this paper.

The synthesis of translucent polymer nanolatexes via microemulsion polymerization.

The potential of an extremely hydrophobic cobalt(II) catalyst for the synthesis of polymer nanolatexes in microemulsion polymerization is investigated. Colloidally stable nanolatexes have been successfully synthesized in microemulsion polymerization of styrene, butyl methacrylate, and 2-ethylhexyl methacrylate and in the presence of bis[(difluoronoryl)-diphenylglyoximato]cobalt(II). The average particle diameter can be reduced from 50 nm to approximately 10 nm in the presence of minor quantities of the cobalt(II) complex. The small particle size, combined with the relatively narrow particle size distribution, results in nanolatexes that are virtually transparent in appearance. Furthermore, the nucleation efficiency can be enhanced by up to two orders of magnitude, corresponding to approximately 1 particle nucleated for every 10(1) micelles. This represents a significant improvement as in microemulsion polymerization generally 1 particle is nucleated for every 10(3) micelles.

Determination of the Critical Chain Length of Oligomers in Dispersion Polymerization.

The critical chain length (jcrit) in dispersion polymerization is systematically investigated utilizing low molecular weight poly(methyl methacrylate) oligomers synthesized by catalytic chain transfer polymerization. The solubility of these oligomers in methanol/water media of different compositions and at different temperatures has been visually determined. The results show that the solubility of the oligomers increases with increasing methanol fraction and increasing temperature. The constructed solubility map allows for an estimate of jcrit as a function of these important polymerization parameters. Furthermore, it is found that the value of jcrit changes with the concentration of the oligomers in the methanol/water medium, an important consideration for understanding the nucleation stage of a dispersion polymerization. The obtained results have been successfully correlated to earlier data reported on the dispersion polymerization of methyl methacrylate.

Free radical copolymerization kinetics of γ-methyl-α-methylene-γ-butyrolactone (MeMBL).

The propagation kinetics and copolymerization behavior of the biorenewable monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL) are studied using the pulsed laser polymerization (PLP)/size exclusion chromatography (SEC) technique. The propagation rate coefficient for MeMBL is 15% higher than that of its structural analogue, methyl methacrylate (MMA), with a similar activation energy of 21.8 kJ·mol(-1). When compared to MMA, MeMBL is preferentially incorporated into copolymers when reacted with styrene (ST), MMA, and n-butyl acrylate (BA); the monomer reactivity ratios fit from bulk MeMBL/ST, MeMBL/MMA, and MeMBL/BA copolymerizations are r(MeMBL) = 0.80 ± 0.04 and r(ST) = 0.34 ± 0.04, r(MeMBL) = 3.0 ± 0.3 and r(MMA) = 0.33 ± 0.01, and r(MeMBL) = 7.0 ± 2.0 and r(BA) = 0.16 ± 0.03, respectively. In all cases, no significant variation with temperature was found between 50 and 90 °C. The implicit penultimate unit effect (IPUE) model was found to adequately fit the composition-averaged copolymerization propagation rate coefficient, k(p,cop), for the three systems.

A new method for the preparation of concentrated translucent polymer nanolatexes from emulsion polymerization.

A novel method for the preparation of concentrated, colloidally stable, translucent polymer nanolatexes is presented. Herein nanolatexes are obtained from emulsion polymerization, utilizing the potential of catalytic chain transfer to enhance the particle nucleation efficiency. Low amounts of emulsifier are required (<8% w/w based on monomer) while the nanolatexes concentration can be increased to 40% w/w. The nanolatexes are translucent in appearance, which was correlated to the average particle size and width of the particle size distribution using Mie theory. Increasing the nanolatex concentration was found to have no deteriorating effect on either the optical or colloidal properties. Preparing translucent nanolatexes via this method is advantageous, as the amount of emulsifier is significantly reduced without sacrificing the optical transparency or the high interfacial surface area of the polymer colloids.

Evaluation of alternative comonomers for the production of ASE and HASE thickeners.

Methyl methacrylate (MMA), n-butyl acrylate (BA) and 2-ethyl hexyl acrylate (EHA) were evaluated as alternatives to ethyl acrylate (EA) in the composition of methacrylic acid (MAA)-EA copolymers for the production of hydrophobically-modified alkali soluble emulsions (HASE). In addition, the impact of Sipomer BEM and PLEX 6954-0 as associative monomers (AM) on the properties of the final HASE products was evaluated. EHA gave reasonable results as a replacement comonomer for alkali soluble emulsion (ASE) synthesis and applications. However, it was not possible to obtain transparent thickened solutions without provoking significant flocculation losses during the synthesis of HASE products that incorporated EHA. MAA-BA and MAA-MMA formulations produced ASE and HASE copolymers with 0.5mol.% AM, which presented high transparency and viscosity levels. When comparing the two AM, it was found that the longer the hydrophobic tail, the higher the apparent viscosity, but the lower the transparency of the final product.

The advantages of in situ surfactant generation for miniemulsions.

The stabilisation of miniemulsions using an in situ generated surfactant is presented. This surfactant, prepared from of a water-soluble base and an oil-soluble long chain acid was successfully used to create stable miniemulsions with up to 60 vol.-% organic phase. It is shown that the creation of a surface active species at the oil-water interface allowed stable miniemulsions to be generated more rapidly than when using conventional surfactant. In addition, polymerised miniemulsions exhibited less secondary nucleation when in situ surfactants were used.