Precipitation polymerization

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IUPAC definition

Polymerization in which monomer(s), initiator(s) and colloid stabilizer(s)
are dissolved in a solvent and this continuous phase that is a nonsolvent for the
formed polymer beyond a critical molecular weight. [1]

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.

After precipitation, the polymerization proceeds by absorption of monomer and initiator into the polymer particles. [2]

A distinction should be made between precipitation and dispersion polymerization, due to the similarities. A dispersion polymerization is actually a type of precipitation polymerization, but the difference lies in the fact that precipitation polymerizations give larger and less regular particles, as a result of little or no stabilizer present. [3]

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Colloid 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. However, some definitions specify that the particles must be dispersed in a liquid, and 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.

An emulsion is a mixture of two or more liquids that are normally immiscible owing to liquid-liquid phase separation. Emulsions are part of a more general class of two-phase systems of matter called colloids. Although the terms colloid and emulsion are sometimes used interchangeably, emulsion should be used when both phases, dispersed and continuous, are liquids. In an emulsion, one liquid is dispersed in the other. Examples of emulsions include vinaigrettes, homogenized milk, liquid biomolecular condensates, and some cutting fluids for metal working.

In polymer chemistry, polymerization, or polymerisation, is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many forms of polymerization and different systems exist to categorize them.

In polymer chemistry, ring-opening polymerization (ROP) is a form of chain-growth polymerization, in which the terminus of a polymer chain attacks cyclic monomers to form a longer polymer. The reactive center can be radical, anionic or cationic. Some cyclic monomers such as norbornene or cyclooctadiene can be polymerized to high molecular weight polymers by using metal catalysts. ROP is a versatile method for the synthesis of biopolymers.

Dispersity

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.

Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant. 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.

Micelle Group of molecules

A micelle or micella is an aggregate of surfactant phospholipid 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.

Suspension (chemistry) 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.

Flocculation Process by which colloidal particles come out of suspension to precipitate as floc or flake

Flocculation, in the field of chemistry, is a process by which colloidal particles come out of suspension to sediment under 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, in a liquid and are not truly dissolved in solution.

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.

Chain-growth polymerization or chain-growth polymerisation is a polymerization technique where unsaturated monomer molecules add onto the active site on a growing polymer chain one at a time. There are a limited number of these active sites at any moment during the polymerization which gives this method its key characteristics.

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.

Robert Gilbert (chemist)

Robert Goulston Gilbert is a polymer chemist whose most significant contributions have been in the field of emulsion polymerisation. In 1970, he gained his PhD from the Australian National University, and worked at the University of Sydney from then until 2006. In 1982, he was elected a fellow of the Royal Australian Chemical Institute; in 1994, he was elected a fellow of the Australian Academy of Science. In 1992, he was appointed full professor, and in 1999 he started the Key Centre for Polymer Colloids, funded by the Australian Research Council, the University and industry. He has served in leadership roles in the International Union of Pure and Applied Chemistry (IUPAC), the world ‘governing body’ of chemistry. He was founding chair (1987–98) of the IUPAC Working Party on the Modelling of Kinetics Processes of Polymerisation, of which he remains a member, and is a member of the IUPAC scientific task groups on starch molecular weight measurements, and terminology. He was vice-president (1996–97) and president (1998–2001) of the IUPAC Macromolecular Division, and secretary of the International Polymer Colloids Group (1997–2001). As of 2007, he is Research Professor at the Centre of Nutrition and Food Science, University of Queensland, where his research program concentrates on the relations between starch structure and nutrition.

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.

A miniemulsion is a special case of emulsion. A miniemulsion is obtained by shearing a mixture comprising two immiscible liquid phases, one or more surfactants and, possibly, one or more co-surfactants.

Suspension polymerization

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.

In chemistry, coalescence is a process in which two phase domains of the same composition come together and form a larger phase domain. In other words, the process by which two or more separate masses of miscible substances seem to "pull" each other together should they make the slightest contact.

Latex Stable dispersion of polymer microparticles in an aqueous medium

Latex is a stable dispersion (emulsion) of polymer microparticles in water. Latexes are found in nature, but synthetic latexes are common as well.

Polymeric materials have widespread application due to their versatile characteristics, cost-effectiveness, and highly tailored production. The science of polymer synthesis allows for excellent control over the properties of a bulk polymer sample. However, surface interactions of polymer substrates are an essential area of study in biotechnology, nanotechnology, and in all forms of coating applications. In these cases, the surface characteristics of the polymer and material, and the resulting forces between them largely determine its utility and reliability. In biomedical applications for example, the bodily response to foreign material, and thus biocompatibility, is governed by surface interactions. In addition, surface science is integral part of the formulation, manufacturing, and application of coatings.

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. 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. With typical precipitation polymerization, the continuous phase is the main locus of polymerization, which is the main difference between precipitation and dispersion.

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. George Odian in Principles of Polymerization third edition, John Wiley and Sons, 1991, pp 302
  3. Joseph C. Salamone in Concise Polymeric Materials Encyclopedia, CRC Press, 1998, pp 1373