Coordination polymerisation is a form of

polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many fo ...

that is catalyzed by transition metal salts and complexes.

Types of coordination polymerization of alkenes

Heterogeneous Ziegler–Natta polymerization

Coordination polymerization started in the 1950s with

heterogeneous Homogeneity and heterogeneity are concepts relating to the uniformity of a substance, process or image. A homogeneous feature is uniform in composition or character (i.e., color, shape, size, weight, height, distribution, texture, language, i ...

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 ...

s based on

titanium tetrachloride Titanium tetrachloride is the inorganic compound with the formula . It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. is a volatile liquid. Upon contact with humid air, it forms thick clouds o ...

and organoaluminium co-catalysts. The mixing of TiCl₄ with trialkylaluminium complexes produces Ti(III)-containing solids that catalyze the polymerization of

ethene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon–carbon double bonds). Ethy ...

and

propene Propylene, also known as propene, is an unsaturated organic compound with the chemical formula . It has one double bond, and is the second simplest member of the alkene class of hydrocarbons. It is a colorless gas with a faint petroleum-like od ...

. The nature of the catalytic center has been of intense interest but remains uncertain. Many additives and variations have been reported for the original recipes.

Homogeneous Ziegler–Natta polymerization

In some applications heterogeneous Ziegler–Natta polymerization has been superseded by

homogeneous Homogeneity and heterogeneity are concepts relating to the uniformity of a substance, process or image. A homogeneous feature is uniform in composition or character (i.e., color, shape, size, weight, height, distribution, texture, language, i ...

catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...

s such as the

Kaminsky catalyst A Kaminsky catalyst is a catalytic system for alkene polymerization. Kaminsky catalysts are based on metallocenes of group 4 transition metals (Ti, Zr, Hf) activated with methylaluminoxane (MAO). These and other innovations have inspired develop ...

discovered in the 1970s. The 1990s brought forward a new range of post-metallocene catalysts. Typical

monomers A monomer ( ; ''wikt:mono-, mono-'', "one" + ''wikt:-mer, -mer'', "part") is a molecule that can chemical reaction, react together with other monomer molecules to form a larger polymer chain or two- or three-dimensional network in a process called ...

are nonpolar ethene and propene. The development of coordination polymerization that enables copolymerization with polar monomers is more recent. Examples of monomers that can be incorporated are methyl vinyl ketones, methyl acrylate, and

acrylonitrile Acrylonitrile is an organic compound with the formula and the structure . It is a colorless, volatile liquid. It has a pungent odor of garlic or onions. Its molecular structure consists of a vinyl group () linked to a nitrile (). It is an im ...

. Kaminsky catalysts are based on

metallocene A metallocene is a compound typically consisting of two cyclopentadienyl anions (, abbreviated Cp) bound to a metallic element, metal center (M) in the oxidation state II, with the resulting general formula Closely related to the metallocenes are ...

s of group 4

metal A metal () is a material that, when polished or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, electricity and thermal conductivity, heat relatively well. These properties are all associated wit ...

s (Ti, Zr, Hf) activated with methylaluminoxane (MAO). Polymerizations catalysed by metallocenes occur via the Cossee–Arlman mechanism. The active site is usually anionic but cationic coordination polymerization also exists. ZNonSingleSite

Specialty monomers

Many alkenes do not polymerize in the presence of Ziegler–Natta or Kaminsky catalysts. This problem applies to polar olefins such as vinyl chloride, vinyl ethers, and acrylate esters.

Butadiene polymerization

The annual production of polybutadiene is 2.1 million tons (2000). The process employs a neodymium-based homogeneous catalyst.

Principles

Coordination polymerization has a great impact on the physical properties of vinyl polymers such as

polyethylene Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic. It is a polymer, primarily used for packaging (plastic bags, plastic films, geomembranes and containers including bott ...

and

polypropylene Polypropylene (PP), also known as polypropene, is a thermoplastic polymer used in a wide variety of applications. It is produced via chain-growth polymerization from the monomer Propene, propylene. Polypropylene belongs to the group of polyolefin ...

compared to the same polymers prepared by other techniques such as free-radical polymerization. The polymers tend to be linear and not branched and have much higher

molar mass In chemistry, the molar mass () (sometimes called molecular weight or formula weight, but see related quantities for usage) of a chemical substance ( element or compound) is defined as the ratio between the mass () and the amount of substance ...

. Coordination type polymers are also stereoregular and can be

isotactic Tacticity (from , "relating to arrangement or order") 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 ...

or syndiotactic instead of just atactic. This

tacticity Tacticity (from , "relating to arrangement or order") 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 ...

introduces

crystallinity Crystallinity refers to the degree of structural order in a solid. In a crystal, the atoms or molecules are arranged in a regular, periodic manner. The degree of crystallinity has a large influence on hardness, density, transparency and diffusi ...

in otherwise

amorphous In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid) is a solid that lacks the long-range order that is a characteristic of a crystal. The terms "glass" and "glassy solid" are sometimes used synonymousl ...

polymers. From these differences in polymerization type the distinction originates between low-density polyethylene (LDPE),

high-density polyethylene High-density polyethylene (HDPE) or polyethylene high-density (PEHD) is a thermoplastic polymer produced from the monomer ethylene. It is sometimes called "alkathene" or " polythene" when used for HDPE pipes. With a high strength-to-density rati ...

(HDPE) or even

ultra-high-molecular-weight polyethylene Ultra-high-molecular-weight polyethylene (UHMWPE, UHMW) is a subset of the thermoplastic polyethylene. Also known as high-modulus polyethylene (HMPE), it has extremely long chains, with a molecular mass typically between 2 and 6 million amu. The l ...

(UHMWPE).

Coordination polymerization of other substrates

Coordination polymerization can also be applied to non-alkene substrates. Dehydrogenative coupling of silanes, dihydro- and trihydrosilanes, to polysilanes has been investigated, although the technology has not been commercialized. The process entails coordination and often oxidative addition of Si-H centers to metal complexes.

Lactide Lactide is the lactone cyclic ester derived by multiple esterification between two (usually) or more molecules from lactic acid (2-hydroxypropionic acid) or other hydroxy carboxylic acid. They are designated as dilactides, trilactides, etc., acc ...

s also polymerize in the presence of

Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any ...

ic catalysts to give polylactide: : Polylactide_synthesis_v

References

{{DEFAULTSORT:Coordination Polymerization Polymerization reactions