Dispersion polymerization

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IUPAC definition

Dispersion polymerization: Precipitation polymerization in which monomer(s),
initiator(s), and colloid stabilizer(s) are dissolved in a solvent forming initially
a homogeneous system that produces polymer and results in the formation of
polymer particles.

Note: The process usually results in polymer particles of colloidal dimensions. [1]

Contents

In polymer science, dispersion polymerization is a heterogeneous polymerization process carried out in the presence of a polymeric stabilizer in the reaction medium. Dispersion polymerization is a type of precipitation polymerization, meaning the solvent selected as the reaction medium is a good solvent for the monomer and the initiator, but is a non-solvent for the polymer. [2] As the polymerization reaction proceeds, particles of polymer form, creating a non-homogeneous solution. In dispersion polymerization these particles are the locus of polymerization, with monomer being added to the particle throughout the reaction. In this sense, the mechanism for polymer formation and growth has features similar to that of emulsion polymerization. [3] With typical precipitation polymerization, the continuous phase (the solvent solution) is the main locus of polymerization, which is the main difference between precipitation and dispersion.

Polymerization mechanism

SEM-Picture of PMMA-particles fabricated by dispersion polymerization after drying / removal of the organic liquid phase (cyclohexane) Dispersionspoly PMMA.tif
SEM-Picture of PMMA-particles fabricated by dispersion polymerization after drying / removal of the organic liquid phase (cyclohexane)

At the onset of polymerization, polymers remain in solution until they reach a critical molecular weight (MW), at which point they precipitate. [4] These initial polymer particles are unstable and coagulate with other particles until stabilized particles form. After this point in the polymerization, growth only occurs by addition of monomer to the stabilized particles. [4] As the polymer particles grow, stabilizer (or dispersant) molecules attach covalently to the surface. These stabilizer molecules are generally graft or block copolymers, and can be preformed or can form in situ during the reaction. [2] Typically, one side of the stabilizer copolymer has an affinity for the solvent while the other side has an affinity for the polymer particle being formed. These molecules play a crucial role in dispersion polymerization by forming a “hairy layer” around the particles that prevents particle coagulation. [4] This controls size and colloidal stability of the particles in the reaction system. The driving force for the particle separation is steric hindrance between the outward-facing tails of the stabilizer layers. [4]

Dispersion polymerization can produce nearly monodisperse polymer particles of 0.1–15 micrometers (µm). This is important because it fills the gap between particle size generated by conventional emulsion polymerization (0.006–0.7 µm) in batch process and that of suspension polymerization (50–1000 µm). [4]

Applications

Particles produced by dispersion polymerization are used in a wide variety of applications. Toners, instrument calibration standards, chromatography column packing materials, liquid crystal display spacers, and biomedical and biochemical analysis all use these micron-size monodisperse particles, particles which were hard to come by before the development of dispersion polymerization methods. [4] The dispersions are also used as surface coatings. Unlike solution coatings, dispersion coatings have viscosities that are independent of polymer MW. The viscosities of dispersions are advantageously lower than those of solutions with practical polymer levels. [4] This allows for easier application of the coating.

One dispersion polymerization system being studied is the use of supercritical liquid carbon dioxide (scCO2) as a solvent. [5] Because of its unique solvent properties, supercritical CO2 is an ideal medium for dispersion polymerization for many soluble-monomer with insoluble-polymer systems. For example, polymers can be separated by releasing the high pressure under which the scCO2 is held. This process is more efficient than typical drying processes. [5] Also, the principles of dispersion polymerization with scCO2 follows principles of green chemistry: low solvent toxicity, low waste, efficient atom economy, and avoidance of purification steps. [5]

Related Research Articles

<span class="mw-page-title-main">Colloid</span> Mixture of an insoluble substance microscopically dispersed throughout another substance

A colloid is a mixture in which one substance consisting of microscopically dispersed insoluble particles is suspended throughout another substance. Some definitions specify that the particles must be dispersed in a liquid, while others extend the definition to include substances like aerosols and gels. The term colloidal suspension refers unambiguously to the overall mixture. A colloid has a dispersed phase and a continuous phase. The dispersed phase particles have a diameter of approximately 1 nanometre to 1 micrometre.

<span class="mw-page-title-main">Polymer</span> Substance composed of macromolecules with repeating structural units

A polymer (;) is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life. Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to biological structure and function. Polymers, both natural and synthetic, are created via polymerization of many small molecules, known as monomers. Their consequently large molecular mass, relative to small molecule compounds, produces unique physical properties including toughness, high elasticity, viscoelasticity, and a tendency to form amorphous and semicrystalline structures rather than crystals.

<span class="mw-page-title-main">Dispersity</span> Measure of heterogeneity of particle or molecular sizes

In chemistry, the dispersity is a measure of the heterogeneity of sizes of molecules or particles in a mixture. A collection of objects is called uniform if the objects have the same size, shape, or mass. A sample of objects that have an inconsistent size, shape and mass distribution is called non-uniform. The objects can be in any form of chemical dispersion, such as particles in a colloid, droplets in a cloud, crystals in a rock, or polymer macromolecules in a solution or a solid polymer mass. Polymers can be described by molecular mass distribution; a population of particles can be described by size, surface area, and/or mass distribution; and thin films can be described by film thickness distribution.

In polymer chemistry, emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomers, and surfactants. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer are emulsified in a continuous phase of water. Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as emulsifiers/stabilizers. The name "emulsion polymerization" is a misnomer that arises from a historical misconception. Rather than occurring in emulsion droplets, polymerization takes place in the latex/colloid particles that form spontaneously in the first few minutes of the process. These latex particles are typically 100 nm in size, and are made of many individual polymer chains. The particles are prevented from coagulating with each other because each particle is surrounded by the surfactant ('soap'); the charge on the surfactant repels other particles electrostatically. When water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles arises because these water-soluble polymers form a 'hairy layer' around a particle that repels other particles, because pushing particles together would involve compressing these chains.

<span class="mw-page-title-main">Micelle</span> Group of fatty molecules suspended in liquid by soaps and/or detergents

A micelle or micella is an aggregate of surfactant amphipathic lipid molecules dispersed in a liquid, forming a colloidal suspension. A typical micelle in water forms an aggregate with the hydrophilic "head" regions in contact with surrounding solvent, sequestering the hydrophobic single-tail regions in the micelle centre.

<span class="mw-page-title-main">Suspension (chemistry)</span> Heterogeneous mixture of solid particles dispersed in a medium

In chemistry, a suspension is a heterogeneous mixture of a fluid that contains solid particles sufficiently large for sedimentation. The particles may be visible to the naked eye, usually must be larger than one micrometer, and will eventually settle, although the mixture is only classified as a suspension when and while the particles have not settled out.

<span class="mw-page-title-main">Flocculation</span> Process by which colloidal particles come out of suspension to precipitate as floc or flake

In colloidal chemistry, flocculation is a process by which colloidal particles come out of suspension to sediment in the form of floc or flake, either spontaneously or due to the addition of a clarifying agent. The action differs from precipitation in that, prior to flocculation, colloids are merely suspended, under the form of a stable dispersion and are not truly dissolved in solution.

Microencapsulation is a process in which tiny particles or droplets are surrounded by a coating to give small capsules, with useful properties. In general, it is used to incorporate food ingredients, enzymes, cells or other materials on a micro metric scale. Microencapsulation can also be used to enclose solids, liquids, or gases inside a micrometric wall made of hard or soft soluble film, in order to reduce dosing frequency and prevent the degradation of pharmaceuticals.

<span class="mw-page-title-main">Electrophoretic deposition</span>

Electrophoretic deposition (EPD), is a term for a broad range of industrial processes which includes electrocoating, cathodic electrodeposition, anodic electrodeposition, and electrophoretic coating, or electrophoretic painting. A characteristic feature of this process is that colloidal particles suspended in a liquid medium migrate under the influence of an electric field (electrophoresis) and are deposited onto an electrode. All colloidal particles that can be used to form stable suspensions and that can carry a charge can be used in electrophoretic deposition. This includes materials such as polymers, pigments, dyes, ceramics and metals.

In materials science, the sol–gel process is a method for producing solid materials from small molecules. The method is used for the fabrication of metal oxides, especially the oxides of silicon (Si) and titanium (Ti). The process involves conversion of monomers into a colloidal solution (sol) that acts as the precursor for an integrated network of either discrete particles or network polymers. Typical precursors are metal alkoxides. Sol-gel process is used to produce ceramic nanoparticles.

In polymer chemistry, free-radical polymerization (FRP) is a method of polymerization by which a polymer forms by the successive addition of free-radical building blocks. Free radicals can be formed by a number of different mechanisms, usually involving separate initiator molecules. Following its generation, the initiating free radical adds (nonradical) monomer units, thereby growing the polymer chain.

An ionomer is a polymer composed of repeat units of both electrically neutral repeating units and ionized units covalently bonded to the polymer backbone as pendant group moieties. Usually no more than 15 mole percent are ionized. The ionized units are often carboxylic acid groups.

Microemulsions are clear, thermodynamically stable isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a cosurfactant. The aqueous phase may contain salt(s) and/or other ingredients, and the "oil" may actually be a complex mixture of different hydrocarbons. In contrast to ordinary emulsions, microemulsions form upon simple mixing of the components and do not require the high shear conditions generally used in the formation of ordinary emulsions. The three basic types of microemulsions are direct, reversed and bicontinuous.

<span class="mw-page-title-main">Particle aggregation</span> Clumping of particles in suspension

Particle agglomeration refers to the formation of assemblages in a suspension and represents a mechanism leading to the functional destabilization of colloidal systems. During this process, particles dispersed in the liquid phase stick to each other, and spontaneously form irregular particle assemblages, flocs, or agglomerates. This phenomenon is also referred to as coagulation or flocculation and such a suspension is also called unstable. Particle agglomeration can be induced by adding salts or other chemicals referred to as coagulant or flocculant.

A dispersion is a system in which distributed particles of one material are dispersed in a continuous phase of another material. The two phases may be in the same or different states of matter.

<span class="mw-page-title-main">Suspension polymerization</span> Polymerization reaction among monomers suspended in a liquid

In polymer chemistry, suspension polymerization is a heterogeneous radical polymerization process that uses mechanical agitation to mix a monomer or mixture of monomers in a liquid phase, such as water, while the monomers polymerize, forming spheres of polymer. The monomer droplets are suspended in the liquid phase. The individual monomer droplets can be considered as undergoing bulk polymerization. The liquid phase outside these droplets help in better conduction of heat and thus tempering the increase in temperature.

Solution polymerization is a method of industrial polymerization. In this procedure, a monomer is dissolved in a non-reactive solvent that contains a catalyst or initiator.

In polymer science, precipitation polymerization is a heterogeneous polymerization process that begins initially as a homogeneous system in the continuous phase, where the monomer and initiator are completely soluble, but upon initiation the formed polymer is insoluble and thus precipitates.

The Stöber process is a chemical process used to prepare silica particles of controllable and uniform size for applications in materials science. It was pioneering when it was reported by Werner Stöber and his team in 1968, and remains today the most widely used wet chemistry synthetic approach to silica nanoparticles. It is an example of a sol-gel process wherein a molecular precursor is first reacted with water in an alcoholic solution, the resulting molecules then joining together to build larger structures. The reaction produces silica particles with diameters ranging from 50 to 2000 nm, depending on conditions. The process has been actively researched since its discovery, including efforts to understand its kinetics and mechanism – a particle aggregation model was found to be a better fit for the experimental data than the initially hypothesized LaMer model. The newly acquired understanding has enabled researchers to exert a high degree of control over particle size and distribution and to fine-tune the physical properties of the resulting material in order to suit intended applications.

Waterborne resins are sometimes called water-based resins. They are resins or polymeric resins that use water as the carrying medium as opposed to solvent or solvent-less. Resins are used in the production of coatings, adhesives, sealants, elastomers and composite materials. When the phrase waterborne resin is used, it usually describes all resins which have water as the main carrying solvent. The resin could be water-soluble, water reducible or water dispersed.

References

  1. Slomkowski, Stanislaw; Alemán, José V.; Gilbert, Robert G.; Hess, Michael; Horie, Kazuyuki; Jones, Richard G.; Kubisa, Przemyslaw; Meisel, Ingrid; Mormann, Werner; Penczek, Stanisław; Stepto, Robert F. T. (2011). "Terminology of polymers and polymerization processes in dispersed systems (IUPAC Recommendations 2011)" (PDF). Pure and Applied Chemistry . 83 (12): 2229–2259. doi:10.1351/PAC-REC-10-06-03. S2CID   96812603.
  2. 1 2 Rudin, A.; Choi, P. (2013). The Elements of Polymer Science and Engineering (3rd ed.). Academic Press. pp. 427–429.
  3. Matyjaszewski, K.; Davis, T. P. (2002). Handbook of Radical Polymerization. John Wiley and Sons. p. 306.
  4. 1 2 3 4 5 6 7 Kawaguchi, S; Ito, K. (2005). "Dispersion Polymerization". Adv Polym Sci. Advances in Polymer Science. 175: 299–328. doi:10.1007/b100118. ISBN   978-3-540-22923-0.
  5. 1 2 3 Jennings, J.; Beija, M.; Kennon, Jeremy T.; et al. (2013). "Advantages of Block Copolymer Synthesis by RAFT-Controlled Dispersion Polymerization in Supercritical Carbon Dioxide". Macromolecules. 46 (17): 6843–6851. Bibcode:2013MaMol..46.6843J. doi: 10.1021/ma401051e .