Chain shuttling polymerization is a dual-

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 ...

method for producing block copolymers with alternating or variable

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 ...

. 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 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 ...

and

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 ...

) have seen widespread use in the

plastics industry The plastics industry manufactures polymer materials—commonly called plastics—and offers services in plastics important to a range of industries, including packaging, building and construction, electronics, aerospace, manufacturing and transpo ...

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 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 density polymers. He also received a Lomonosov Gold Medal in 19 ...

. Ziegler discovered the original Titanium based catalyst essential for olefin polymerization, while Natta used the catalyst to alter and control the

stereochemistry Stereochemistry, a subdiscipline of chemistry, studies the spatial arrangement of atoms that form the structure of molecules and their manipulation. The study of stereochemistry focuses on the relationships between stereoisomers, which are defined ...

(tacticity) of the olefin polymers (hence

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 ...

). By controlling the tacticity of the polymer, a chain can, for example, either be semi

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, macrosc ...

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 ...

, rigid or elastic, heat resistant or have a low

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 rub ...

. Much research since has been dedicated to predicting and creating polymers based on this work.

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 transf ...

is the term coined to describe the use of specially made catalysts (often involving transition metal centers) in olefin polymerization, since the polymer chains self-propagate in the presence of the catalyst until intentionally terminated. Living polymerization, however, produces only one type of tacticity per catalyst. While the specific tacticity can be controlled by altering the type of catalyst used, creating a block copolymer requires that the polymerization be terminated, the catalyst destroyed, and that the chain re-propagate using another catalyst that produces the desired stereochemistry. Such manipulations are usually difficult, however.

Method

Chain shuttling polymerization makes use of two catalysts and a chain shuttling agent (CSA) to generate copolymers of alternating

. Catalyst 1 (Cat1) propagates a polyolefin of a desired tacticity. Catalyst 2 (Cat2) generates another chain of a different tacticity. The two chains are allowed to co-propagate in a single reactor in the same living polymer fashion as before. To alternate the tacticity, a CSA will transfer the polymer chain from its respective catalyst. The CSA can then bind to Cat2 and attach the chain to Cat2. When the chain attaches to Cat2, the polymerization of that chain continues, except it now propagates with the tacticity dictated by Cat2, not Cat1. The general result is that the chain will alternate between two different tacticities. As the forward and reverse reactions occur, the polymer chain is “shuttled” back and forth between the two catalysts and a block copolymer is formed.Gibson, V. “Shuttling Polyolefins to a New Materials Dimension” Science Vol. 312 May 2006 The shuttling of chains back and forth from catalysts via a CSA can be viewed as a competing

chemical equilibrium In a chemical reaction, chemical equilibrium is the state in which both the Reagent, reactants and Product (chemistry), products are present in concentrations which have no further tendency to change with time, so that there is no observable chan ...

. Note that the forward and reverse reactions of CSA binding and leaving either Cat1 or Cat2 are possible. This competition means that a chain can leave Cat1 via a CSA and the reattach to Cat1, polymerizing the same tacticity. The rate at which the reattachment of Cat1 occurs can be controlled by altering the relative concentrations of Cat1, Cat2 and CSA. For example, if one wanted to produce a polymer with the properties mainly resulting from the use of Cat1 and only wanted to influence its properties slightly by the presence of Cat2, a greater concentration of Cat1 would be used than for Cat2. The rate of alternation between tacticity can be controlled by altering the concentration of CSA relative to Cat1 and Cat2; having a higher concentration of CSA means that the chains will shuttle back and forth more rapidly, creating shorter units of alternating tacticity.

Advantages

The first clear advantage of chain shuttling is that one can design copolymers with more desirable traits. A polymer that is normally semi crystalline and rigid can be altered so that it has a lower glass transition temperature. An amorphous, elastic polymer membrane can be altered to have a higher melting point. The technique opens the door for tailor-made polymers to be widely accessible and simple to make inexpensively.

References

{{reflist Polymer chemistry