On the reaction characteristics of miniemulsion polymerization with aqueous phase initiation experiments and modeling tom g. This in turn lowers the effective termination rate k t,eff and termination rate r t and thus, the average number. Miniemulsion polymerization and the structure of polymer. Principles and applications of emulsion polymerization. Recent developments in miniemulsion polymerization.
The influence of the initiation on droplet nucleation is conflicting and it has not been completely considered. Online reading principles of polymerization book are very easy. When finally processed to provide the function for which the latex was selected. Miniemulsion polymerization as a versatile tool for the synthesis of functionalized polymers. Xray diffraction xrd and transmission electron microscopy tem indicated that the clay platelets were mostly exfoliated in the paraffin wax at low concentrations, and partially exfoliated at high concentrations. The properties of eva copolymer highly depend on the percentage of ethylene in the copolymer. According to this mechanism, a minimum amount of fatty alcohol is needed to. Living radical polymerization in miniemulsion using reversible additionfragmentation chain transfer. Kaler center for molecular and engineering thermodynamics, department of chemical engineering, university of delaware, newark, delaware 19716. Most miniemulsion polymerizations are carried out in batch reactors.
Although several polymerization processes have been adopted along the years, suspension, emulsion and miniemulsion systems deserve special attention due to its ability to produce spherical polymer. A small vial with an inner diameter of 12 mm was used to run a miniemulsion with 3 ml volume, whereas a larger vial with a diameter of 25 mm contained 10 ml of miniemulsion figure s1. Only a fraction of the surfactant and reaction time that was necessary in the conventional emulsion polymerization is required. It summarizes the recent advances in miniemulsion polymerization technology including the advances on the selection of surfactants and cosurfactants, the expansion of miniemulsion technology in various polymers and copolymer systems, and. This file is licensed under the creative commons attributionshare alike 4. Jilin woodbased materials science and engineering key laboratories jilin, china corresponding author. Moreover, the viscosity of the reaction mixture is reduced. The thermal polymerization of 1,3cyclopentadiene by way of the dielsalder addition is not an important polymerization, but it does provide a simple concrete example of how a monomer and a polymer are related.
Polymerization kinetics and the evolution of the molecular weight distribution mwd were followed during the synthesis of different aba block copolymers. Free download principles of polymerization book now is available, you just need to subscribe to our book vendor, fill the registration form and the digital book copy will present to you. As shown in figure s4, the particle size of polymers. Preparation of nanometer silicaacrylate composite emulsion through miniemulsion polymerization fapeng wang 1,2, xingwei he 1, weikun xu 1, shenyuan fu 1 and jiuyin pang 2. Some developments in miniemulsion polymerization aiming at taking advantage of its unique mechanisms minimizing the drawbacks of this technique are discussed. From the calorimetric data, it could be observed that only styrenebased co polymerization followed typical miniemulsion polymerization mechanism. In principle, the synthesis of functionalized polymers in miniemulsion can occur either by. Polymers products that are commonly referred to as plastics by the general public are known to chemists as polymers.
Particle nucleation using different initiators in the miniemulsion polymerization of styrene 193 brazilian journal of chemical engineering vol. Supporting information for encapsulated dyepolymer. Miniemulsion polymerization and the structure of polymer and. Synthesis of phosphonatefunctionalized polystyrene and.
A miniemulsion also known as nanoemulsion is a special case of emulsion. In principle, the synthesis of functionalized polymers in miniemulsion can occur either by copolymerizing one or several functional monomers, or by the. Principles of polymerization download free pdf books or. A 5dimensional smithewart based model is developed to understand differences for reversible additionfragmentation chain transfer raft miniemulsion polymerization with theoretical agents mimicking cases of slow fragmentation, crosstermination, and ideal exchange while accounting for chain length and monomer conversion dependencies due to diffusional limitations.
In this procedure, a monomer is dissolved in a nonreactive solvent that contains a catalyst the reaction results in a polymer which is also soluble in the chosen solvent. Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant. Heat released by the reaction is absorbed by the solvent, and so the reaction rate is reduced. The miniemulsion technique is a particular case in the family of heterophase polymerizations, which allows the formation of functionalized polymers by polymerization or modification of polymers in stable nanodroplets. Uptodate coverage of methods of emulsion polymerization this book provides a comprehensive reference on emulsion polymerization methods,focusing on the fundamental mechanisms and kinetics of each process, as well as howthey can be applied to the manufacture of environmentally friendly polymeric materials. Miniemulsion polymerization as a versatile tool for the synthesis of. Submissions are welcome on fundamental experimental or theoretical investigations of emulsion polymerization and related heterogeneous polymerizations including miniemulsion, microemulsion, suspension and inverse emulsion, on control of emulsion polymerization at the molecular or colloidal level, on application of emulsion polymerization for. The monomer miniemulsions herein include, in addition to water, a surfactant, and a monomer or mixture thereof, one or more polymers which function as a polymeric cosurfactant. In miniemulsion polymerization, particles are formed via monomer droplet nucleation, whereas. The second part deals with the application of miniemulsion polymerization for. Solution polymerization is a method of industrial polymerization. The model predictions are verified against data taken from the literature. Miniemulsion copolymerization of ethylene and vinyl acetate.
High molecular weight polymers can be made at fast polymerization rates. Abstract in miniemulsion polymerization, droplet nucleation is the key factor to ensure the production of polymer particles with a desired composition. Miniemulsion polymerization was initially used for the synthesis of the ablock, which forms hard domains, followed by 2eha preemulsion feeding to build the bblock soft domains. The main obstacle remains the preparation of a chemically.
Miniemulsion polymerization has recently exploded in terms of publications and the development of a wide range of useful polymer materials only accessible through this polymerization technique. Azo polymerization initiators comprehensive catalog. Mar 16, 2010 faridimajidi r, sharifisanjani n 2007 emulsifierfree miniemulsion polymerization of styrene and the investigation of encapsulation of nanoparticles with polystyrene via this procedure using an anionic initiator. The reaction kinetics and final particle sizes were compared for homopolymerizations and copolymerizations of the two monomers. By contrast, in bulk and solution freeradical polymerization, there is a tradeoff between molecular weight and polymerization rate the continuous water phase is an excellent conductor of heat, enabling fast polymerization rates without loss of temperature control. Miniemulsion polymerization as a versatile tool for. The miniemulsion process allows the formation of complex structured polymeric nanoparticles and the encapsulation of a solid or liquid, an inorganic or organic, or a hydrophobic or hydrophilic material into a polymer shell. An approach to control copolymer composition miniemulsion polymerization. The composite latex and the resultant film were characterized by fourier transformation infrared spectroscopy. In the first stage of the polymerization, emulsification of the monoroers is important, because insufficient emulsification influences the product properties. On the miniemulsion polymerization of very hydrophobic monomers. Miniemulsion polymerization technology wiley online books. Preparation of nanometer silicaacrylate composite emulsion. Normally, only hydrophilic monomers can be polymerized with this initiating system in water or a co.
In this study, we show that miniemulsion photopolymerization provides a suitable method to create latex without the apparent addition of these three compounds. It should be used in place of this raster image when not inferior. Abstract the miniemulsion technique is a particular case in the family of heterophase polymerizations, which allows the formation of func. Population balance model, miniemulsion, polymerization miniemulsions are comprised of relatively stable. This mechanism has been confirmed in aibn initiated miniemulsion polymeriza tions using various monomerwater ratios. Faridimajidi r, sharifisanjani n 2007 emulsifierfree miniemulsion polymerization of styrene and the investigation of encapsulation of nanoparticles with polystyrene via this procedure using an anionic initiator. Hybrid nanostructured particles via surfactantfree double. Similarly, sodium acrylate was polymerized in inverse. This in turn lowers the effective termination rate k t,eff and termination rate r t and thus, the average number weight of polymerization pn increases. This is due to the fact that once poor emulsification has affected the polymerization. Encapsulation by miniemulsion polymerization springerlink. Miniemulsion polymerization matyjaszewski polymer group.
The use of miniemulsion ringopening metathesis polymerization romp to form polyunsaturated latexes is still a largely unexplored field. Cannot be used for polymers whose glass transition temperature is less than the polymerization temperature, or else aggregation will occur. Another advantage of miniemulsion systems compared to solution polymerization was demonstrated by qi et al. The main objective of this mqp was to follow the reaction kinetics of the polymerization reaction of mma in miniemulsions. Chemical engineering 160260 polymer science and engineering. Enhanced polymerization rates were seen for the miniemulsion polymerizations. At the initial stage of the polymerization the reaction system consists of emulsifier micelles, pmp and large monomer droplets. From the calorimetric data, it could be observed that only styrenebased copolymerization followed typical miniemulsion polymerization mechanism. Pscobawaxclay nanocomposites via miniemulsion polymerization. Deterministic modeling of raft bulk and miniemulsion polymerization up to high monomer conversion dries j. Preparation of polymer composite latex via miniemulsion.
In theory, a miniemulsion comprises the ideal environment for living radical polymerization by the raft process. Photoinduced miniemulsion atom transfer radical polymerization. Effects of stirring rates and dodecyl mercaptan on nanocapsules containing noctadecane prepared by miniemulsion polymerization xuejing zhang, xingxiang zhang, jianping wang,ming you state key laboratory of hollow fiber membrane materials and processes,tianjin polytechnic unive rsity, tjpu tianjin, p r china email. For raft miniemulsion polymerization of styrene mediated by polystyryl. However, continuous reactors or continuous reactor trains can provide a high level of consistency when operated at steady state. An essentially stable monomer miniemulsion characterized by small monomer droplet size is prepared and is then polymerized to a polymer latex under free radical polymerization conditions. A polymer is a macromolecule which consists of small molecular units that are repeated over and over again to form a long chain. Emulsion polymerization is a usual process of a radical polymerization, its features are explained by the fact that the main site of reactions micelles and pmp have discrete volumes. Miniemulsion copolymerization of ethylene and vinyl acetate juchen guo, kyu yong choi, f. Polymers free fulltext mechanical and morphological. The discussion includes preparation of highly concentrated latexes, miniemulsion polymerization in continuous stirred tank reactors cstrs, and elimination of the low.
The monomer miniemulsions herein include, in addition to water, a surfactant, and a monomer or mixture thereof, one or more polymers which function as a. Compartmentalization minimizes radicalradical termination events and droplet nucleation eliminates the mass. The silicapolyacylate composite latex was prepared via miniemulsion polymerization. Deterministic modeling of raft bulk and miniemulsion. Living radical polymerization in miniemulsion using. Elaassep emulsion polymers institute and department of chemical. A population balance model for the miniemulsion polymerization that incorporates the particle size distribution is developed in this work. Raft miniemulsion polymerization targeting to polymer of higher. S1 supporting information for encapsulated dyepolymer nanoparticles prepared via miniemulsion polymerization for inkjet printing jingjing li, jiangli fan, rui cao, zhen zhang, jianjun du, and xiaojun peng and state key laboratory of fine chemicals. The effect of the ultrasound power was investigated herein.
Principles of polymerization free book download also nice conclusion after you had successfully register to our book vendor. Miniemulsion polymerization as a versatile tool for the. Miniemulsion polymerization is the process of converting these monomer droplets into polymer particles. Preparation of multiphase polystyrenecobutyl acrylatewax. The miniemulsion polymerization is not subject to this limitation.
Sds was dissolved in 140 g deionized water, then adding a preparation of nanometer silicaacrylate composite emulsion through miniemulsion polymerization fapeng wang1,2, xingwei he1, weikun xu1, shenyuan fu1 and jiuyin pang2. Kinetics of polymerization reaction in miniemulsions a major. The most common type of emulsion polymerization is an oilinwater emulsion, in which droplets of monomer the oil are emulsified with surfactants in a continuous phase of water. The heat flow time curves of copolymerization of styrene with vpa differ from the styrene homopolymerization, which is due to the difference in water solubility of the monomers. As a consequence of the mechanism of the formation of miniemulsions, and due to their colloidal properties and stability, a large range of different polymers. Raft mechanism with upon modeling no explicit calculation. Miniemulsion polymerization is different from conventional emulsion polymerization because it employs a miniemulsification process achieved via ultrasonic or highshear treatment. The effect of fluorinated acrylate on stability of the composite latex was compared with the traditional costabilizer. Our reader mostly like to read principles of polymerization book in pdf epub kindle format. The percent polymer was calculated once the samples were freezedried, which removed the monomer and left only the. Synthesis of phosphonatefunctionalized polystyrene and poly. Miniemulsion polymerization of styrene wiley online library.
Continuous macroemulsion and miniemulsion polymerization of methyl methacrylate. Effects of stirring rates and dodecyl mercaptan on. Modeling of miniemulsion polymerization of styrene with. Dhooge, ghent university, belgium reversible addition fragmentation chain transfer raft polymerization is an important. The initiator potassium peroxodisulfate kps could not be used due to its low solubility in the 2hydroxyethyl methacrylate monomer. A population balance model for miniemulsion polymerization. Miniemulsion polymerization technology comprises 10 papers by many of the worlds experts on the subject.
This was done by carrying out mma miniemulsion polymerization reactions and taking samples at different times. Well over 100 billion pounds of polymer are produced each year, and it is expected that this. Dec 01, 2010 the miniemulsion technique is a particular case in the family of heterophase polymerizations, which allows the formation of functionalized polymers by polymerization or modification of polymers in stable nanodroplets. Fluorinated acrylate monomer was used the costabilizer and hydrophobic modifier. The copolymer latexes composed mainly of a high content of. Us5686518a miniemulsion polymerization process using. Jul 12, 2010 miniemulsion polymerization technology comprises 10 papers by many of the worlds experts on the subject.
Joseph schork introduction ethylenevinyl acetate copolymer eva is a commercially important polymer that has been used in a wide range of applications. Miniemulsion polymerization of acrylated methyl oleate for pressure. Jan 29, 2008 uptodate coverage of methods of emulsion polymerization this book provides a comprehensive reference on emulsion polymerization methods,focusing on the fundamental mechanisms and kinetics of each process, as well as howthey can be applied to the manufacture of environmentally friendly polymeric materials. Effects of stirring rates and dodecyl mercaptan on nanocapsules containing noctadecane prepared by miniemulsion polymerization xuejing zhang, xingxiang zhang, jianping wang,ming you state key laboratory of hollow fiber membrane materials and processes,tianjin polytechnic unive rsity, tjpu tianjin, p r china. A miniemulsion is obtained by shearing a mixture comprising two immiscible liquid phases for example, oil and water, one or more surfactants and, possibly, one or more cosurfactants typical examples are hexadecane or cetyl alcohol. China wako chemicals gmbh germany wako chemicals usa, inc. Synthesis of nanoscale materials through miniemulsion. The copolymerization of vinyl acetate vac and vinyl 2. Miniemulsion polymerization and the structure of polymer and hybrid nanoparticles.