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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.
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.
Tacticity is the relative stereochemistry of adjacent chiral centers within a macromolecule. The practical significance of tacticity rests on the effects on the physical properties of the polymer. The regularity of the macromolecular structure influences the degree to which it has rigid, crystalline long range order or flexible, amorphous long range disorder. Precise knowledge of tacticity of a polymer also helps understanding at what temperature a polymer melts, how soluble it is in a solvent and its mechanical properties.
Size-exclusion chromatography, also known as molecular sieve chromatography, is a chromatographic method in which molecules in solution are separated by their size, and in some cases molecular weight. 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.
A macromolecule is a very large molecule important to biological processes, such as a protein or nucleic acid. It is composed of thousands of covalently bonded atoms. Many macromolecules are polymers of smaller molecules called monomers. The most common macromolecules in biochemistry are biopolymers and large non-polymeric molecules such as lipids, nanogels and macrocycles. Synthetic fibers and experimental materials such as carbon nanotubes are also examples of macromolecules.
In theoretical chemistry, a conjugated system is a system of connected p-orbitals with delocalized electrons in a molecule, which in general lowers the overall energy of the molecule and increases stability. It is conventionally represented as having alternating single and multiple bonds. Lone pairs, radicals or carbenium ions may be part of the system, which may be cyclic, acyclic, linear or mixed. The term "conjugated" was coined in 1899 by the German chemist Johannes Thiele.
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.
Polymer chemistry is a sub-discipline of chemistry that focuses on the structures of chemicals, chemical synthesis, and chemical and physical properties of polymers and macromolecules. The principles and methods used within polymer chemistry are also applicable through a wide range of other chemistry sub-disciplines like organic chemistry, analytical chemistry, and physical chemistry. Many materials have polymeric structures, from fully inorganic metals and ceramics to DNA and other biological molecules. However, polymer chemistry is typically related to synthetic and organic compositions. Synthetic polymers are ubiquitous in commercial materials and products in everyday use, such as plastics, and rubbers, and are major components of composite materials. Polymer chemistry can also be included in the broader fields of polymer science or even nanotechnology, both of which can be described as encompassing polymer physics and polymer engineering.
Adhesion is the tendency of dissimilar particles or surfaces to cling to one another.
Paul John Flory was an American chemist and Nobel laureate who was known for his work in the field of polymers, or macromolecules. He was a leading pioneer in understanding the behavior of polymers in solution, and won the Nobel Prize in Chemistry in 1974 "for his fundamental achievements, both theoretical and experimental, in the physical chemistry of macromolecules".
Chain-growth polymerization (AE) or chain-growth polymerisation (BE) 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.
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.
In polymer chemistry, an ideal chain is the simplest model to describe polymers, such as nucleic acids and proteins. It assumes that the monomers in a polymer are located at the steps of a hypothetical random walker that does not remember its previous steps. By neglecting interactions among monomers, this model assumes that two monomers can occupy the same location. Although it is simple, its generality gives insight about the physics of polymers.
The worm-like chain (WLC) model in polymer physics is used to describe the behavior of polymers that are semi-flexible: fairly stiff with successive segments pointing in roughly the same direction, and with persistence length within a few orders of magnitude of the polymer length. The WLC model is the continuous version of the Kratky–Porod model.
Flory–Huggins solution theory is a lattice model of the thermodynamics of polymer solutions which takes account of the great dissimilarity in molecular sizes in adapting the usual expression for the entropy of mixing. The result is an equation for the Gibbs free energy change for mixing a polymer with a solvent. Although it makes simplifying assumptions, it generates useful results for interpreting experiments.
The persistence length is a basic mechanical property quantifying the bending stiffness of a polymer. The molecule behaves like a flexible elastic rod/beam. Informally, for pieces of the polymer that are shorter than the persistence length, the molecule behaves like a rigid rod, while for pieces of the polymer that are much longer than the persistence length, the properties can only be described statistically, like a three-dimensional random walk.
Rubber elasticity refers to a property of crosslinked rubber: it can be stretched by up to a factor of 10 from its original length and, when released, returns very nearly to its original length. This can be repeated many times with no apparent degradation to the rubber. Rubber is a member of a larger class of materials called elastomers and it is difficult to overestimate their economic and technological importance. Elastomers have played a key role in the development of new technologies in the 20th century and make a substantial contribution to the global economy. Rubber elasticity is produced by several complex molecular processes and its explanation requires a knowledge of advanced mathematics, chemistry and statistical physics, particularly the concept of entropy. Entropy may be thought of as a measure of the thermal energy that is stored in a molecule. Common rubbers, such as polybutadiene and polyisoprene, are produced by a process called polymerization. Very long molecules (polymers) are built up sequentially by adding short molecular backbone units through chemical reactions. A rubber polymer follows a random, zigzag path in three dimensions, intermingling with many other rubber molecules. An elastomer is created by the addition of a few percent of a cross linking molecule such as sulfur. When heated, the crosslinking molecule causes a reaction that chemically joins (bonds) two of the rubber molecules together at some point. Because the rubber molecules are so long, each one participates in many crosslinks with many other rubber molecules forming a continuous molecular network. As a rubber band is stretched, some of the network chains are forced to become straight and this causes a decrease in their entropy. It is this decrease in entropy that gives rise to the elastic force in the network chains.
In polymer chemistry, a repeat unit or repeating unit is a part of a polymer whose repetition would produce the complete polymer chain by linking the repeat units together successively along the chain, like the beads of a necklace.
Tethered particle motion (TPM) is a biophysical method that is used for studying various polymers such as DNA and their interaction with other entities such as proteins.
References
- ↑ Contour length (in polymers) IUPAC Compendium of Chemical Terminology, 2nd Edition, 1997