Chain Shuttling Polymerization
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Chain Shuttling Polymerization
Chain shuttling polymerization is a dual-catalyst method for producing block copolymers with alternating or variable tacticity. The desired effect of this method is to generate hybrid polymers that bear the properties of both polymer chains, such as a high melting point accompanied by high elasticity. It is a relatively new method, the first instance of its use being reported by Arriola et al. in May 2006. Olefin polymerization Olefin polymers (such as polypropylene and polyethylene) have seen widespread use in the plastics industry in the past 50 years. A way to enhance the properties of these olefin polymers was first discovered by the scientists Karl Ziegler and Giulio Natta. Ziegler discovered the original Titanium based catalyst essential for olefin polymerization, while Natta used the catalyst to alter and control the stereochemistry (tacticity) of the olefin polymers (hence Ziegler–Natta catalyst). By controlling the tacticity of the polymer, a chain can, for exam ...
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Catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst. Catalysis may be classified as either homogeneous, whose components are dispersed in the same phase (usually gaseous or liquid) as the reactant, or heterogeneous, whose components are not in the same phase. Enzymes and other biocatalysts are often considered as a third category. Catalysis is ubiquitous in chemical industry of all kinds. Estimates are that 90% of all commercially produced chemical products involve catalysts at some s ...
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Ziegler–Natta Catalyst
A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the synthesis of polymers of 1-alkenes (alpha-olefins). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility: * Heterogeneous supported catalysts based on titanium compounds are used in polymerization reactions in combination with cocatalysts, organoaluminum compounds such as triethylaluminium, Al(C2H5)3. This class of catalyst dominates the industry. * Homogeneous catalysts usually based on complexes of the group 4 metals titanium, zirconium or hafnium. They are usually used in combination with a different organoaluminum cocatalyst, methylaluminoxane (or methylalumoxane, MAO). These catalysts traditionally contain metallocenes but also feature multidentate oxygen- and nitrogen-based ligands. Ziegler–Natta catalysts are used to polymerize terminal alkenes (ethylene and alkenes with the vinyl double bond): :''n'' CH2=CHR → − H2−CHRsub>' ...
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Chemical Equilibrium
In a chemical reaction, chemical equilibrium is the state in which both the reactants and products are present in concentrations which have no further tendency to change with time, so that there is no observable change in the properties of the system. This state results when the forward reaction proceeds at the same rate as the reverse reaction. The reaction rates of the forward and backward reactions are generally not zero, but they are equal. Thus, there are no net changes in the concentrations of the reactants and products. Such a state is known as dynamic equilibrium. Historical introduction The concept of chemical equilibrium was developed in 1803, after Berthollet found that some chemical reactions are reversible. For any reaction mixture to exist at equilibrium, the rates of the forward and backward (reverse) reactions must be equal. In the following chemical equation, arrows point both ways to indicate equilibrium. A and B are reactant chemical species, S and T are p ...
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Chain Shuttling Diagram
A chain is a serial assembly of connected pieces, called links, typically made of metal, with an overall character similar to that of a rope in that it is flexible and curved in compression but linear, rigid, and load-bearing in tension. A chain may consist of two or more links. Chains can be classified by their design, which can be dictated by their use: * Those designed for lifting, such as when used with a hoist; for pulling; or for securing, such as with a bicycle lock, have links that are torus shaped, which make the chain flexible in two dimensions (the fixed third dimension being a chain's length). Small chains serving as jewellery are a mostly decorative analogue of such types. * Those designed for transferring power in machines have links designed to mesh with the teeth of the sprockets of the machine, and are flexible in only one dimension. They are known as roller chains, though there are also non-roller chains such as block chains. Two distinct chains can b ...
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Chain Transfer
Chain transfer is a polymerization Chemical reaction, reaction by which the activity of a growing polymer chain is transferred to another molecule. :P• + XR' → PX + R'• Chain transfer reactions reduce the average molecular weight of the final polymer. Chain transfer can be either introduced deliberately into a polymerization (by use of a ''chain transfer agent'') or it may be an unavoidable side-reaction with various components of the polymerization. Chain transfer reactions occur in most forms of addition polymerization including radical polymerization, ring-opening polymerization, coordination polymerization, and cationic polymerization, as well as anionic polymerization. Types Chain transfer reactions are usually categorized by the nature of the molecule that reacts with the growing chain. * Transfer to chain transfer agent. Chain transfer agents have at least one weak chemical bond, which therefore facilitates the chain transfer reaction. Common chain transfer age ...
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Living Polymerization
In polymer chemistry, living polymerization is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed. This can be accomplished in a variety of ways. Chain termination and chain transfer reactions are absent and the rate of chain initiation is also much larger than the rate of chain propagation. The result is that the polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar (i.e. they have a very low polydispersity index). Living polymerization is a popular method for synthesizing block copolymers since the polymer can be synthesized in stages, each stage containing a different monomer. Additional advantages are predetermined molar mass and control over end-groups. Living polymerization is desirable because it offers precision and control in macromolecular synthesis. This is important since many of the novel/useful properties of polymers result from t ...
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Glass Transition Temperature
The glass–liquid transition, or glass transition, is the gradual and reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle "glassy" state into a viscous or rubbery state as the temperature is increased. ISO 11357-2: Plastics – Differential scanning calorimetry – Part 2: Determination of glass transition temperature (1999). An amorphous solid that exhibits a glass transition is called a glass. The reverse transition, achieved by supercooling a viscous liquid into the glass state, is called vitrification. The glass-transition temperature ''T''g of a material characterizes the range of temperatures over which this glass transition occurs (as an experimental definition, typically marked as 100 s of relaxation time). It is always lower than the melting temperature, ''T''m, of the crystalline state of the material, if one exists. Hard plastics like polystyrene and poly(methyl methacrylate) are u ...
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Amorphous
In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid, glassy solid) is a solid that lacks the long-range order that is characteristic of a crystal. Etymology The term comes from the Greek ''a'' ("without"), and ''morphé'' ("shape, form"). In some older articles and books, the term was used synonymously with glass. Today, "glassy solid" or "amorphous solid" is considered the overarching concept. Polymers are often amorphous. Structure Amorphous materials have an internal structure comprising interconnected structural blocks that can be similar to the basic structural units found in the corresponding crystalline phase of the same compound. Unlike crystalline materials, however, no long-range order exists. Localized order in amorphous materials can be categorized as short or medium range order. By convention, short range order extends only to the nearest neighbor shell, typically only 1-2 atomic spacings. Medium range order is then de ...
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Crystalline
A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macroscopic single crystals are usually identifiable by their geometrical shape, consisting of flat faces with specific, characteristic orientations. The scientific study of crystals and crystal formation is known as crystallography. The process of crystal formation via mechanisms of crystal growth is called crystallization or solidification. The word ''crystal'' derives from the Ancient Greek word (), meaning both "ice" and "rock crystal", from (), "icy cold, frost". Examples of large crystals include snowflakes, diamonds, and table salt. Most inorganic solids are not crystals but polycrystals, i.e. many microscopic crystals fused together into a single solid. Polycrystals include most metals, rocks, ceramics, and ice. A third category of s ...
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Stereochemistry
Stereochemistry, a subdiscipline of chemistry, involves the study of the relative spatial arrangement of atoms that form the structure of molecules and their manipulation. The study of stereochemistry focuses on the relationships between stereoisomers, which by definition have the same molecular formula and sequence of bonded atoms (constitution), but differ in structural formula (the three-dimensional orientations of their atoms in space). For this reason, it is also known as 3D chemistry—the prefix "stereo-" means "three-dimensionality". Stereochemistry spans the entire spectrum of organic, inorganic, biological, physical and especially supramolecular chemistry. Stereochemistry includes methods for determining and describing these relationships; the effect on the physical or biological properties these relationships impart upon the molecules in question, and the manner in which these relationships influence the reactivity of the molecules in question ( dynamic stereochemis ...
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Copolymer
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. Commercial copolymers include acrylonitrile butadiene styrene (ABS), styrene/butadiene co-polymer (SBR), nitrile rubber, styrene-acrylonitrile, styrene-isoprene-styrene (SIS) and ethylene-vinyl acetate, all of which are formed by chain-growth polymerization. Another production mechanism is step-growth polymerization, which is used to produce the nylon-12/6/66 copolymer of nylon 12, nylon 6 and nylon ...
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Giulio Natta
Giulio Natta (26 February 1903 – 2 May 1979) was an Italian chemical engineer and Nobel laureate. He won a Nobel Prize in Chemistry in 1963 with Karl Ziegler for work on high polymers. He also received a Lomonosov Gold Medal in 1969. Biography Early years Natta was born in Imperia, Italy. He earned his degree in chemical engineering from the Politecnico di Milano university in Milan in 1924. In 1927 he passed the exams for becoming a professor there. From 1929 to 1933, he was also in charge of physical chemistry at the Faculty of Sciences of the University of Milan. In 1933 he became a full professor and the director of the Institute of General Chemistry of Pavia University, where he stayed until 1935. During this time he began using crystallography to elucidate the structures of a wide variety of molecules including phosphine, arsine and others. In that year he was appointed full professor in physical chemistry at the University of Rome. Career From 1936 to 1938 he moved as ...
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