Catalyst for living radical polymerization

A polymerization method comprising a step of conducting a living radical polymerization, wherein the living radical polymerization step is conducted in the presence of a catalyst and an organic halide having a carbon-halogen bond, wherein the catalyst reversibly produces a radical from the organic halide having a carbon-halogen bond, and

• the catalyst consists of a compound comprising
• at least one central element consisting of carbon and
• a halogen atom binding to the central element,
• wherein the compound is represented by the following general formula (Ia):
• wherein
• Ra is halogen, or an organic group having a double or triple bond;
• when Ra has a double or triple bond, one of the atoms constituting the double or triple bond is bound to the carbon of the central element in the aforementioned formula Ia;
• Rb is halogen, or an organic group having a double or triple bond;
• when Rb has a double or triple bond, one of the atoms constituting the double or triple bond is bound to the carbon of the central element in the aforementioned formula Ia;
• Rc is halogen, hydrogen, or an organic group having a double or triple bond;
• when Rc has a double or triple bond, one of the atoms constituting the double or triple bond is bound to the carbon of the central element in formula Ia;
• Ra and Rb may be linked to each other such that Ra, Rb, and the central element form a ring;
• Ra and Rc may be linked to each other such that Ra, Rc, and the central element form a ring;
• Rb and Rc may be linked to each other such that Rb, Rc, and the central element form a ring;
• Ra, Rb, and Rc may be linked to one another such that Ra, Rb, and Rc form a ring;
• Xa is halogen;
• Ra and Rb may be taken together with the carbon atom of the central element to form an unsaturated aliphatic ring structure;
• and
• Ra, Rb, and Rc may be taken together with the carbon atom of the central element to form an aromatic ring structure, and
• wherein the method does not use a catalyst for living radical polymerization containing Ge, Sn, or Sb as a central element.

A polymerization method comprising a step of conducting a living radical polymerization, wherein the living radical polymerization step is conducted in the presence of a catalyst and an organic halide having a carbon-halogen bond wherein the catalyst reversibly produces a radical from the organic halide having a carbon-halogen bond, and

• wherein the catalyst comprises:
• at least one central element consisting of carbon and
• a halogen atom binding to the central element,
• wherein the central element is further bound to two or three electron-donating substituents capable of stabilizing a carbon radical that is generated by elimination of the halogen atom from the central element;
• wherein when the number of substituents is two, the two substituents may be linked to each other such that the central element and the two substituents form a ring structure, and
• when the number of substituents is three, two of the three substituents may be linked to each other such that the two linked substituents and the central element form a ring structure, or the three substituents may be linked to one another to form a ring structure, and
• wherein the method does not use a catalyst for living radical polymerization containing Ge, Sn, or Sb as a central element.

A method of conducting a living radical polymerization, the method comprising:

• reacting a radical generated from a radical initiator with a catalyst precursor compound to generate an activated radical;
• and
• polymerizing a monomer having a radical-reactive unsaturated bond using the activated radical to obtain a polymer,
• wherein the precursor compound has a carbon atom which becomes a central element, and the carbon atom which becomes the central element is bound to one or two hydrogen atoms, and bound to two or three substituents that are taken together with the central element to form a resonance structure;
• wherein when the number of substituents is two, the two substituents may be linked to each other such that the central element and the two substituents form a ring structure,
• when the number of substituents is three, two of the three substituents may be linked to each other such that the central element and the two linked substituents form a ring structure, or the three substituents may be linked to one another to form a ring structure;
• a radical generated from the radical initiator abstracts a hydrogen atom from the carbon atom of the central element in the precursor compound to generate the activated radical;
• the activated radical acts as a catalyst for a living radical polymerization in the polymerization reaction of the monomer;
• the activated radical, which is generated after the abstraction of the hydrogen atom, is stabilized by a resonance structure formed by the central element and the substituents which are taken together.