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 66, as well as the copolyester family. Copolymers can be used to develop commercial goods or drug delivery vehicles.

copolymer: A polymer derived from more than one species of monomer. (See Gold Book entry for note.)

Since a copolymer consists of at least two types of constituent units (also structural units), copolymers can be classified based on how these units are arranged along the chain. Linear copolymers consist of a single main chain and include alternating copolymers, statistical copolymers, and block copolymers. Branched copolymers consist of a single main chain with one or more polymeric side chains, and can be grafted, star shaped, or have other architectures.

The reactivity ratio of a growing copolymer chain terminating in a given monomer is the ratio of the reaction rate constant for addition of the same monomer and the rate constant for addition of the other monomer. That is, ${\displaystyle r_{1}={\frac {k_{11}}{k_{12}}}}$ and ${\displaystyle r_{2}={\frac {k_{22}}{k_{21}}}}$, where for example ${\displaystyle k_{12}}$ is the rate constant for propagation of a polymer chain ending in monomer 1 (or A) by addition of monomer 2 (or B).

The composition and structural type of the copolymer depend on these reactivity ratios r₁ and r₂ according to the Mayo–Lewis equation, also called the copolymerization equation or copolymer equation, for the relative instantaneous rates of incorporation of the two monomers.

${\displaystyle {\frac {\mathrm {d} \left[\mathrm {M} _{1}\right]}{\mathrm {d} \left[\mathrm {M} _{2}\right]}}={\frac {\left[\mathrm {M} _{1}\right]\left(r_{1}\left[\mathrm {M} _{1}\right]+\left[\mathrm {M} _{2}\right]\right)}{\left[\mathrm {M} _{2}\right]\left(\left[\mathrm {M} _{1}\right]+r_{2}\left[\mathrm {M} _{2}\right]\right)}}}$

Block copolymers comprise two or more homopolymer subunits linked by covalent bonds. The union of the homopolymer subunits may require an intermediate non-repeating subunit, known as a junction block. Diblock copolymers have two distinct blocks; triblock copolymers have three. Technically, a block is a portion of a macromolecule, comprising many units, that has at least one feature which is not present in the adjacent portions. A possible sequence of repeat units A and B in a triblock copolymer might be ~A-A-A-A-A-A-A-B-B-B-B-B-B-B-A-A-A-A-A~.