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Polymers are chainlike molecules that are made of the same repetition unit. With a few exceptions such as proteins, a polymer consists of a mix of molecules with different chain lengths. Therefore, average values are given for the molecular weight like the number average, the weight average or the viscosity average molar mass. A measure for the width of the molecular weight distribution is the polydispersity index. The targeted manipulation of the molecular weight distribution of a polymer by removing short and/or long chain material is called polymer fractionation.
The molecular weight of polymers has a large influence on their properties and therefore determines the applications. Among others the flow behavior, the solubility, the mechanical properties but also the lifetime are influenced by the molecular weight. For high duty polymers – polymers that have to fulfill elevated demands – not only the molecular weight but also the molecular weight distribution is important. This especially holds true if low and/or high molecular material disturbs a given task.
Polymers can be fractionated on an analytical scale by size exclusion chromatography (SEC), Matrix-assisted laser desorption/ionization (MALDI) or field flow fractionation (FFF). These methods are used to determine the molecular weight distribution.
In most cases the fractionation of polymers on a preparative scale is based on chromatographic methods (e.g. preparative SEC or Baker-Williams fractionation). Therefore, the production is normally limited to few grams only. For large scales of several grams up to kg or even tons the “continuous spin fractionation” can be used. F. Francuskiewicz gives an overview about preparative polymer fractionation.
Agarose is a heteropolysaccharide, generally extracted from certain red algae. It is a linear polymer made up of the repeating unit of agarobiose, which is a disaccharide made up of D-galactose and 3,6-anhydro-L-galactopyranose. Agarose is one of the two principal components of agar, and is purified from agar by removing agar's other component, agaropectin.
A polymer is a substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeating subunits derived from one or more species of monomers. 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.
Size-exclusion chromatography, also known as molecular sieve chromatography, is a chromatographic method in which molecules in solution are separated by their shape, and in some cases size. It is usually applied to large molecules or macromolecular complexes such as proteins and industrial polymers. Typically, when an aqueous solution is used to transport the sample through the column, the technique is known as gel-filtration chromatography, versus the name gel permeation chromatography, which is used when an organic solvent is used as a mobile phase. The chromatography column is packed with fine, porous beads which are commonly composed of dextran, agarose, or polyacrylamide polymers. The pore sizes of these beads are used to estimate the dimensions of macromolecules. SEC is a widely used polymer characterization method because of its ability to provide good molar mass distribution (Mw) results for polymers.
Polyacrylamide gel electrophoresis (PAGE) is a technique widely used in biochemistry, forensic chemistry, genetics, molecular biology and biotechnology to separate biological macromolecules, usually proteins or nucleic acids, according to their electrophoretic mobility. Electrophoretic mobility is a function of the length, conformation, and charge of the molecule. Polyacrylamide gel electrophoresis is a powerful tool used to analyze RNA samples. When polyacrylamide gel is denatured after electrophoresis, it provides information on the sample composition of the RNA species.
In chemistry, the molar mass of a chemical compound is defined as the ratio between the mass and the amount of substance of any sample of the compound. The molar mass is a bulk, not molecular, property of a substance. The molar mass is an average of many instances of the compound, which often vary in mass due to the presence of isotopes. Most commonly, the molar mass is computed from the standard atomic weights and is thus a terrestrial average and a function of the relative abundance of the isotopes of the constituent atoms on Earth. The molar mass is appropriate for converting between the mass of a substance and the amount of a substance for bulk quantities.
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.
Gel permeation chromatography (GPC) is a type of size-exclusion chromatography (SEC), that separates high molecular weight or colloidal analytes on the basis of size or diameter, typically in organic solvents. The technique is often used for the analysis of polymers. As a technique, SEC was first developed in 1955 by Lathe and Ruthven. The term gel permeation chromatography can be traced back to J.C. Moore of the Dow Chemical Company who investigated the technique in 1964. The proprietary column technology was licensed to Waters Corporation, who subsequently commercialized this technology in 1964. GPC systems and consumables are now also available from a number of manufacturers. It is often necessary to separate polymers, both to analyze them as well as to purify the desired product.
In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are sometimes called bipolymers. Those obtained from three and four monomers are called terpolymers and quaterpolymers, respectively. Copolymers can be characterized by a variety of techniques such as NMR spectroscopy and size-exclusion chromatography to determine the molecular size, weight, properties, and composition of the material.
In polymer chemistry, step-growth polymerization refers to a type of polymerization mechanism in which bi-functional or multifunctional monomers react to form first dimers, then trimers, longer oligomers and eventually long chain polymers. Many naturally-occurring and some synthetic polymers are produced by step-growth polymerization, e.g. polyesters, polyamides, polyurethanes, etc. Due to the nature of the polymerization mechanism, a high extent of reaction is required to achieve high molecular weight. The easiest way to visualize the mechanism of a step-growth polymerization is a group of people reaching out to hold their hands to form a human chain—each person has two hands. There also is the possibility to have more than two reactive sites on a monomer: In this case branched polymers production take place.
In polymer chemistry, the molar mass distribution describes the relationship between the number of moles of each polymer species and the molar mass of that species. In linear polymers, the individual polymer chains rarely have exactly the same degree of polymerization and molar mass, and there is always a distribution around an average value. The molar mass distribution of a polymer may be modified by polymer fractionation.
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.
The degree of polymerization, or DP, is the number of monomeric units in a macromolecule or polymer or oligomer molecule.
The Melt Flow Index (MFI) is a measure of the ease of flow of the melt of a thermoplastic polymer. It is defined as the mass of polymer, in grams, flowing in ten minutes through a capillary of a specific diameter and length by a pressure applied via prescribed alternative gravimetric weights for alternative prescribed temperatures. Polymer processors usually correlate the value of MFI with the polymer grade that they have to choose for different processes, and most often this value is not accompanied by the units, because it is taken for granted to be g/10min. Similarly, the test conditions of MFI measurement are normally expressed in kilograms rather than any other units. The method is described in the similar standards ASTM D1238 and ISO 1133.
In polymer chemistry, chain transfer is a polymerization reaction by which the activity of a growing polymer chain is transferred to another molecule:
Absolute molar mass is a process used to determine the characteristics of molecules.
Field-flow fractionation, abbreviated FFF, is a separation technique invented by J. Calvin Giddings. The technique is based on separation of colloidal or high molecular weight substances in liquid solutions, flowing through the separation platform, which does not have a stationary phase. It is similar to liquid chromatography, as it works on dilute solutions or suspensions of the solute, carried by a flowing eluent. Separation is achieved by applying a field or cross-flow, perpendicular to the direction of transport of the sample, which is pumped through a long and narrow laminar channel. The field exerts a force on the sample components, concentrating them towards one of the channel walls, which is called accumulation wall. The force interacts with a property of the sample, thereby the separation occurs, in other words, the components show differing "mobilities" under the force exerted by the crossing field. As an example, for the hydraulic, or cross-flow FFF method, the property driving separation is the translational diffusion coefficient or the hydrodynamic size. For a thermal field, it is the ratio of the thermal and the translational diffusion coefficient.
Polymer characterization is the analytical branch of polymer science.
Crystallization of polymers is a process associated with partial alignment of their molecular chains. These chains fold together and form ordered regions called lamellae, which compose larger spheroidal structures named spherulites. Polymers can crystallize upon cooling from melting, mechanical stretching or solvent evaporation. Crystallization affects optical, mechanical, thermal and chemical properties of the polymer. The degree of crystallinity is estimated by different analytical methods and it typically ranges between 10 and 80%, with crystallized polymers often called "semi-crystalline". The properties of semi-crystalline polymers are determined not only by the degree of crystallinity, but also by the size and orientation of the molecular chains.
In polymer chemistry and polymer physics, the Flory–Fox equation is a simple empirical formula that relates molecular weight to the glass transition temperature of a polymer system. The equation was first proposed in 1950 by Paul J. Flory and Thomas G. Fox while at Cornell University. Their work on the subject overturned the previously held theory that the glass transition temperature was the temperature at which viscosity reached a maximum. Instead, they demonstrated that the glass transition temperature is the temperature at which the free space available for molecular motions achieved a minimum value. While its accuracy is usually limited to samples of narrow range molecular weight distributions, it serves as a good starting point for more complex structure-property relationships.
In polymer chemistry, an organogel is a class of gel composed of an organic liquid phase within a three-dimensional, cross-linked network. Organogel networks can form in two ways. The first is classic gel network formation via polymerization. This mechanism converts a precursor solution of monomers with various reactive sites into polymeric chains that grow into a single covalently-linked network. At a critical concentration, the polymeric network becomes large enough so that on the macroscopic scale, the solution starts to exhibit gel-like physical properties: an extensive continuous solid network, no steady-state flow, and solid-like rheological properties. However, organogels that are "low molecular weight gelators" can also be designed to form gels via self-assembly. Secondary forces, such as van der Waals or hydrogen bonding, cause monomers to cluster into a non-covalently bonded network that retains organic solvent, and as the network grows, it exhibits gel-like physical properties. Both gelation mechanisms lead to gels characterized as organogels.