Deposition of polymer latices on grafted Nylon 6 fiber

Deposition of polymer latices on a grafted Nylon 6 fiber was studied as a function of pH and the degree of grafting. The latices were polystyrene (PS), styrene/acrylamide copolymer (P(St/AAm)) and styrene/acrylic acid copolymer (P(St/AA)). The deposition of the latices on the grafted fiber decreased in every case with increasing pH and no deposition was observed at alkaline pH. The grafting of fiber with acrylic and methacrylic acid reduced the deposition of P(St/AAm) and P(St/AA) latices but had no influence on the deposition of PS latex. The relation between the deposition rates and the interaction energy at acidic pH indicates that the deposition of PS latex on the grafted fiber mainly depends on the electrostatic interaction. These results suggest that the expansion of water-soluble polyelectrolyte layer on the surface of grafted fiber plays an important role on the deposition.     

Application of Molecular Weight and Particle Growth Measurements in Continuously Uniform Latices to Kinetic Studies of Styrene Emulsion Polymerization

It is possible to generate, in specially formulated styrene emulsion polymerizations, latices in which the monomer—polymer particles are uniform through all stages of growth. These latices are kinetically similar to their polydispersed counterparts and can therefore be used as model systems in generalized kinetic studies of emulsion polymerization. The most important feature of these systems is the fact that the particles are uniform throughout the reaction with regard to all intrinsic properties and rate processes, and the particles can be characterized by this complete, continuous uniformity. Certain remarkably simple, but precise, relationships exist between the overall, measurable kinetic parameters and the individual particle kinetic parameters, thereby resulting in a heretofore unrealized analytic accessibility. Molecular weight kinetic analyses are an order of magnitude more accurate than in non-uniform systems. Application of these continuously uniform systems in actual kinetic studies indicates an inconsistency in the current concepts of emulsion polymerization, i.e., the generation of polymer at a constant molecular weight is predicted while an increase of several fold is observed. Before the situation can be clarified, further studies with continuously uniform systems are needed to evaluate molecular weight development, molecular weight distribution, and molecular structure and also to re-evaluate the rate and diffusion processes which control these structural features.     

Synthesis and characterization of sulphonated core-shell latices in the size range between 30 and 80 nm

The objective of the current work was the synthesis of sulphonated core-shell nanolatices and to investigate to which extend it is possible to control the final surface charge of such latices. For this purpose differently sized polystyrene seed latices with average diameters in the size range between 30 and 80 nm were synthesized by emulsion polymerization. To obtain the final latices, a sulphonated comonomer was incorporated in the outer surface shell of the particles by further reaction of the seed latices with styrene and sodium styrene sulphonate (NaSS). In a first test series the seed latex surface was modified with four different amounts of NaSS. In a second test series four different seed latices were reacted with the same amount of NaSS. In the last set of reactions the seed latices were reacted with different amounts of NaSS and in these reactions the ratio of added NaSS to the specific surface area of the seed latex was kept constant to obtain differently sized latices of the same surface charge density. The yield of sulphonic acid groups in the particle shell was found between 57 and 74% after an intensive cleaning step by ion exchange. The results show possibilities for a reproducible synthesis of small sulphonated latex particles with a desired surface charge density.     

Preparation and characterization of polysiloxane-poly(butyl acrylate-styrene) composite latices and their film properties

Gamma ray induced seeded emulsion co-polymerization of styrene and butyl acrylate was carried out in the presence of polymerizable polysiloxane seed latex which was obtained by the ring opening co-polymerization of octamethyl cyclotetrasiloxane (D₄) and tetramethyl tetravinyl cyclotetrasiloxane (VD₄) catalyzed by dodecylbenzene sulphonic acid (DBSA). A series of polysiloxane seed latices with different molecular weight, vinyl content, and particle size were used. The conversion-time curve showed that the polymerization rate was accelerated much by the seed latex. The obtained composite latices also showed good storage stability, mechanical stability and high electrolyte resistance ability. The morphology of the composite latex particles was found to be a quite uniform fine structure by transmission electron microscope (TEM). The graft polymerization between polymerizable polysiloxane and butyl acrylate or styrene was confirmed by the Fourier transform infrared spectroscopy (FT-IR) and the graft efficiency was also studied. The influence of seed content, molecular weight, vinyl content of the polysiloxane and seed latex particles size to the mechanical performance, water absorption ratio, surface properties, transparency and UV resistance of the latex films, was also investigated.     

Multiphase Polymer Dispersions and Nanocomposites by Catalytic/Free Radical Emulsion Polymerization

Summary: Free radical emulsion polymerization of styrene (S) or butyl acrylate (BA) in the presence of latices of linear polyethylene (PE) prepared by catalytic emulsion polymerization affords colloidally stable multiphase latices. Coagulation of a PE/PS latex affords nanocomposites composed of small PE phases dispersed in a PS matrix, as evidenced by the large supercoolings of PE crystallization (by DSC). TEM of PE/PBA latices indicates a PBA phase around the PE particles under the emulsion polymerization conditions investigated. Films formed from these dispersions exhibit homogeneously dispersed PE particles.

Multiphase latices are obtained by free radical emulsion polymerization of butyl acrylate in the presence of latices of linear polyethylene (PE) prepared by catalytic emulsion polymerization.     

Polymeric surfactants from styrene‐co‐maleic‐anhydride copolymers

Polymeric surfactants are usually prepared via copolymerisation of suitably substituted monomers. In this study, polymer surfactants were made by modifying a highly functionalized polymer chain back bone: a copolymer of styrene and maleic anhydride, SMA (34wt.‐% MA), was turned into anionic, cationic and nonionic surfactants by saponification and imidation of the MA functions. In some cases, the chains were partly hydrophobized by stearyl substituents. All surfactants were water soluble without forming hydrogels. To different degrees, they proved themselves as dispersants and thickeners. Carbon black and titanium dioxide were excellently dispersed by the ionic derivatives of SMA while latices were particularly well thickened by hydrophobized nonionic derivatives.     

Polystyrene latices containing dodecanamide‐modified poly(propyleneimine) dendrimers

Polymerization of styrene in aqueous dispersions of the dodecanamide derivative of poly(propyleneimine) dendrimer DAB‐dendr‐(NH₂)₆₄ and sodium dodecyl sulfate (SDS) produced stable latices. With initial SDS concentrations of 10 mM or less, molar ratios of SDS to dendrimer end groups ranging from 2.3:1 to 9.5:1, and less than 10 wt % of SDS relative to styrene, the polystyrene latices had diameters of 30–60 nm and coefficients of variation of diameters of less than 10% when measured by transmission electron microscopy. Higher concentrations of SDS gave more polydisperse latices. The polystyrene latices formed with SDS and the dodecanamide‐modified dendrimer were almost the same size and polydispersity as those formed with SDS and the parent primary amine dendrimer DAB‐dendr‐(NH₂)₆₄. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 597–605, 2003     

The morphology of the monomer–polymer particle in styrene emulsion polymerization

A heterogeneous model for the monomer–polymer particle in styrene emulsion polymerization is presented. In this model, the growing particle consists of an expanding polymer-rich core surrounded by a monomer-rich shell which serves as the major locus of polymerization. This core-shell model was suggested by kinetic studies with continuously uniform latices which showed that the systems of interest were of the Smith-Ewart case II type but that the dynamic—as opposed to equilibrium swelling—particle monomer concentrations were continuously variable. Supporting evidence for the suggested morphology was obtained by electron microscope observation of ultrathin sections of latex particles.     

Participation of electrolyte cations in albumin adsorption onto negatively charged polymer latices

The participation of electrolyte cations in the adsorption of bovine serum albumin (BSA) onto polymer latices was investigated. The latices used were hydrophobic polystyrene (PS), and hydrophilic copolymers, i.e., styrene (St)/2-hydroxyethyl methacrylate(HEMA) copolymer [P(St/HEMA)] and styrene/acrylamide (AAm) copolymer [P(St/AAm)]. Three kinds of electrolyte cations (Na⁺, Ca²⁺, Mg²⁺) were used as the chloride. The amount of BSA adsorbed in every cation medium showed a maximum near the isoelectric point (iep, pH about 5) of the protein. The amounts of BSA adsorbed onto copolymer latices (except in the acidic pH region lower than the iep) were considerably smaller than that onto PS latex because of the steric repulsion and the decrease in the hydrophobic interaction between BSA and copolymer latices. In the acidic pH region, there was little difference in the amount of BSA adsorbed in every cation medium. However, in the pH region higher than the iep, the amounts of BSA adsorbed (particularly onto PS latex) in divalent cations (Ca²⁺ and Mg²⁺) media were relatively greater compared with that in a monovalent (Na⁺) one. This result was interpreted on the basis of the differences in such effects of electrolyte cations as dehydration power, suppression of the electrostatic repulsion, and binding affinity to BSA molecule. Ion Chromatographic estimation of the amounts of electrolyte cations captured upon BSA adsorption (in pH > 5) revealed that divalent cations were incorporated into the contact interface between the latex and BSA molecule so as to prevent the accumulation of anion charge and facilitate the protein adsorption.     

Synthesis of polystyrene latex with amphoteric surfactant and its characterization

An emulsion polymerization of styrene in the presence of an amphoteric surfactant; N,N-dimethyl-n-laurylbetaine (LNB) was carried out at pH 7.0. The polymerization rate and the concentration of the latex particle were proportional to the LNB concentration of 0.6 power. The latex particle sizes became smaller with increasing concentrations of LNB. The molecular weights of polystyrene latices increased with the concentration of LNB. The zeta-potentials of latex particles were significantly dependent on the pH, and showed the existence of an isoelectric point.     

Nanostructured latexes made by a sequential multistage emulsion polymerization

A series of linear and lightly crosslinked nanostructured latices was prepared by a sequential multistage semicontinuous emulsion polymerization process alternating styrene (S) and n‐butyl acrylate (BA) monomer feeds five times, that is ten stages, and vice versa, along with several control latices. Transmission electron micrographs of the RuO₄‐stained cross sections of nanostructured and copolymer latex particles and films showed that their particle morphologies were not very different from each other, but the nanostructured latex particles were transformed into a nanocomposite film containing both polystyrene (PS) and poly(n‐butyl acrylate) (PBA) nanodomains interconnected by their diffuse polymer mixtures (i.e. interlayers). The thermal mechanical behaviors of the nanostructured latex films showed broad but single T_gs slightly higher than those of their counterpart copolymer films. These single T_gs indicated that their major component phases were the diffuse interlayers and that they behaved like pseudopolymer alloys. The minimum film formation temperatures of nanostructured latices capped with PBA and PS, respectively, were 15 °C lower than and equal to those of their counterpart copolymer latices, but their T_gs were about 10 °C higher. Consequently, nanostructured latices enabled us to combine good film formation with high strengths for adhesives and coatings applications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2826–2836, 2006     

A one-pot method for the preparation of latices of telechelic oligomers,by ozonolysis of latices of polymers containing main-chain unsaturation

Poly(methyl methacrylate-co-butadiene), Poly(butyl methacrylate-co-butadiene) and Poly(methyl methacrylate-co-2,3-dimethyl butadiene) latices (a.k.a. latexes) were prepared by monomer-starved emulsion polymerization. The polymerizations were followed by GPC. It was found that the molecular-weight distribution did not alter significantly with conversion if the polymerizations were carried out at a feed rate of 0.03 cm³ s⁻¹ per 1000 cm³ of reaction medium and a temperature of 70°C. Slower rates of monomer addition led to broadening of the molecular-weight distribution. The resultant latices were swollen with varying amounts of toluene. Ozonolysis of the swollen and nonswollen latices yielded latices of polymer ozonides. Oxidation, with selenium oxide/hydrogen peroxide reagent, converted the ozonides to latices of carboxylic acid or methyl ketone ended telechelic oligomers. It was found that the molecular weights of the oligomers were a function of toluene concentration. Colloidal stability was found to be a function of end-group structure. Thus, carboxylic acid end groups impart extra stability to the colloid while methyl ketone end groups do not. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3255–3262, 1997     

The use of selected acrylate and acrylamide-based surfmers and polysoaps in the emulsion polymerization of styrene

Polymerizable surfactants (surfmers) 12-acryloyloxy-dodecanoic acid and 11-acrylamidoundecanoic acid and their respective sodium salts were prepared and then polymerized to form their corresponding oligomers using reversible addition-fragmentation chain transfer (RAFT). Different concentrations of both the surfmers, their sodium salts, and their RAFT oligomers were used as polysoaps in the emulsion polymerization of styrene. Stabilities of the pre-emulsions before polymerization were determined and compared. After polymerization, particle sizes and polydispersities of the resulting polystyrene latices were determined. Sodium dodecyl sulfate (SDS) was used as a reference surfactant to compare the particle sizes and stabilities of the pre-emulsions prepared using surfmers and polymeric surfactants (polysoaps) as particle stabilizers. Emulsion polymerization of styrene using these surfmers and polysoaps all led to latices which were stable for a period of more than six months, as indicated by constant particle sizes, whereas latices prepared using the conventional surfactant, SDS, were not as stable.     

Reversible‐addition fragmentation chain transfer radical emulsion polymerization by a nanoprecipitation process

Polymerizations of styrene under emulsion reversible‐addition fragmentation chain transfer polymerization conditions are reported. Using a recently developed nanoprecipitaiton process, emulsion particles were formed by the precipitation of an acetone solution of a macroRAFT agent into an aqueous solution of poly(vinyl alcohol). The particles were then swollen with monomer and subsequently polymerized. Emulsion polymerizations were performed at 65 and 75 °C in which either KPS, BPO, or a combination of both was used as an initiating source. Reactions were also performed at temperatures over 100 °C in which the thermal initiation of styrene was used as an initiating source. In all cases, the polymerizations proceeded in a living manner, yielding polymers that showed an incremental increase in molecular weight with time and had narrow molecular weight distributions. Plots of number‐ average molecular weight versus conversion were linear, indicating a controlled polymerization. The resulting latices were colloidally stable and gave particle size distributions with a typical average particle diameter in the 150 nm range. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5708–5718, 2006     

Interaction of pigments with polystyrene latex prepared using a zwitterionic emulsifier

An emulsion polymerization of styrene in the presence of a zwitterionic emulsifier,N,N-dimethyl-n-laurylbetaine (LNB), was carried out at pH 7.0. The stability of mixed dispersions composed of latex particles prepared with the emulsifier (LNB) and titanium dioxide particles was studied as a function of pH. The zeta potential of the synthesized latex particles was significantly dependent on the pH and showed the existence of an isoelectric point. In the pH range of 3.0–8.3, where the latices are positively charged while titanium dioxide pigment particles are negatively charged, the mixed suspensions of the latices and titanium dioxide particles were dispersed but exhibited heterocoagulation with increasing particle number of the latices. Furthermore, titanium dioxide particles were restabilized with further addition of the latices. The mechanisms of these processes are discussed. A similar experiment was conducted with silica particles.     

Dual-phase solid polymer electrolytes prepared from styrene–butadiene copolymer latices

A new dual-phase solid polymer electrolyte system has been proposed. In this system, a network of ion pathways is formed in a low-polarity, host polymer matrix. A series of electrolytes were prepared from styrene-butadiene copolymer latices with dissolved lithium salts. Polymer films were formed from these latices, and then impregnated with γ-butyrolactone (γ-BL) or γ-butyrolactone/dimethoxyethane mixture (γ-BL/DME), giving latex polymer electrolytes. The ionic conductivity of the polymer electrolyte system increased with increasing solvent content, although a distinct percolation threshold was not measured. Ionic conductivity also increased with the use of DME cosolvent, with the highest conductivity being 1.4 × 10^?4S/cm. Complex impedance diagrams are discussed. The diagrams show significant deviations from the ideal. TEM/SEM observations are consistent with the desired dual-phase morphology. © 1993 John Wiley & Sons, Inc.     

Viscoelastic behaviour of butyl acrylate/styrene/2-hydroxyethyl methacrylate/acrylic acid latices thickened with associative thickeners

The rheological behaviour of butyl acrylate/styrene/acrylic acid latices thickened with a hydrophobically modified ethoxylated polyurethane (HEUR) or hydrophobically modified alkali-soluble polyacrylate emulsion (HASE) was investigated. While the pseudoplastic character of frequency dependence of complex viscosity was similar for both thickeners, viscoelastic behaviour, expressed as the ratio of loss and storage moduli, significantly differed, indicating that the HEUR molecules, unlike swollen HASE particles, create a viscoelastic space structure. The increase in hydrophilicity of the particle surface, achieved by incorporation of 2-hydroxyethyl methacrylate (HEMA) monomer into the latex copolymer reduced the viscoelasticity of latices thickened with HEUR, but not of those thickened with HASE. This confirms that adsorption of hydrophobic end-groups on particle surface is important for thickening of latices with HEUR and that a physical network of latex particles interconnected by the thickener macromolecules is formed. To cite this article: O. Quadrat et al., C. R. Chimie 6 (2003).     

Emulsion and controlled miniemulsion polymerization of the renewable monomer γ‐methyl‐α‐methylene‐γ‐butyrolactone

The kinetics of free‐radical emulsion polymerization of γ‐methyl‐α‐methylene‐γ‐butyrolactone (MeMBL), a renewable monomer related to methyl methacrylate, are presented in detail for the first time, and stable polymer latices are prepared. The effects of different reaction parameters on free‐radical emulsion polymerization of MeMBL are presented. Homogeneous nucleation is asserted to be the dominant path for particle formation. Miniemulsion copolymerization of MeMBL and styrene is also reported. In this case, the homogeneous nucleation process appears limited when using an oil soluble initiator. Both the RAFT miniemulsion polymerizations and RAFT bulk polymerizations are well controlled and narrow polydispersity copolymers are produced. Rate retardation is observed in the RAFT miniemulsion polymerizations compared with the free‐radical polymerization and RAFT bulk polymerizations and the possible causes of the retardation are discussed. The reactivity ratios of MeMBL and styrene in RAFT bulk copolymerization are also determined. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5929–5944, 2008     

Aqueous Catalytic Polymerization of Olefins

Catalytic conversions in aqueous environments by transition metal complexes have become a well‐established field over the past two decades. However, the vast majority of investigations have focussed on small‐molecule synthesis. This may appear somewhat surprising as water is a particularly attractive reaction medium, especially for polymerization reactions. For example, aqueous emulsion and suspension polymerization is carried out today on a large scale by noncatalytic free‐radical routes. Polymer latices can be obtained as a product, that is, stable aqueous dispersions of polymer particles in the size range of 50 to 1000 nm. Such latices possess a unique property profile. Amongst other advantages, the use of water as a dispersing medium is particularly environmentally friendly. In comparison to these free‐radical reactions, aqueous catalytic polymerizations of olefinic monomers have received less attention. However, considerable advances and an increased awareness of this field have emerged during the past few years. A variety of high molecular weight polymers ranging from amorphous or semicrystalline polyolefins to polar‐substituted hydrophilic materials have now been prepared by catalytic polymerization of olefinic monomers in water. Polymer latices based on a number of readily available monomers are accessible and catalytic activities as high as 10⁵ turnovers per hour have already been reported. As another example, materials prepared by aqueous catalytic polymerization have been investigated as protein inhibitors. A versatile field spanning colloids, polymer, and coordination chemistry has emerged.