The present application relates to a method of performing living cationic polymerization of monomers by supermolecular anion-binding catalysis. It uses various simple Bronsted acids or adducts thereof with a monomer as the cationic initiator, and various hydrogen bond donors as the catalyst for binding and dissociating counter anions dynamically, to living and controlled polymerize one or more cationically polymerizable monomers to form a homopolymer or a copolymer. In the present application, the hydrogen-bond donor can exert non-covalent anion-binding interactions to dynamically and reversibly activate dormant covalent bond under mild conditions, in turn to precisely control the equilibrium between dormant covalent precursors and active cationic species, thereby achieving the precise control of the polymer's molecular weight, distribution and end group structure, and solving the environment-unfriendly relevant problems in traditional metal-based Lewis acid catalysis, which include extreme low polymerization temperature, restrict anhydrous requirement of the reaction, strict purification requirement of the monomer and catalysis-initiating system, metal residue in polymer or the like.

The present application relates to a method of performing living cationic polymerization of monomers by supermolecular anion-binding catalysis. It uses various simple Bronsted acids or adducts thereof with a monomer as the cationic initiator, and various hydrogen bond donors as the catalyst for binding and dissociating counter anions dynamically, to living and controlled polymerize one or more cationically polymerizable monomers to form a homopolymer or a copolymer. In the present application, the hydrogen-bond donor can exert non-covalent anion-binding interactions to dynamically and reversibly activate dormant covalent bond under mild conditions, in turn to precisely control the equilibrium between dormant covalent precursors and active cationic species, thereby achieving the precise control of the polymer's molecular weight, distribution and end group structure, and solving the environment-unfriendly relevant problems in traditional metal-based Lewis acid catalysis, which include extreme low polymerization temperature, restrict anhydrous requirement of the reaction, strict purification requirement of the monomer and catalysis-initiating system, metal residue in polymer or the like.

Acido-basic properties of a system containing a polymer obtained by decomposing by oxidative cleavage of a carbon-carbon double bond, and a trifunctional molecule having an alkoxysilyl group in the structure as represented by the formula (A) are changed such that the system is changed into a basic system when the system is acidic and the system is changed into an acidic system when the system is basic to combine the decomposed polymer and the trifunctional molecule, thereby introducing the alkoxysilyl group into the main chain. Furthermore, acido-basic properties of a system containing a polymer obtained by decomposing by oxidative cleavage of a carbon-carbon double bond to decrease the molecular weight, and a functional molecule having an alkoxysilyl group as represented by the formula (a) are changed in the same manner as above to combine the decomposed polymer and the functional molecule, thereby introducing the alkoxysilyl group in a molecular terminal. ##STR00001##

Acido-basic properties of a system containing a polymer obtained by decomposing by oxidative cleavage of a carbon-carbon double bond, and a trifunctional molecule having an alkoxysilyl group in the structure as represented by the formula (A) are changed such that the system is changed into a basic system when the system is acidic and the system is changed into an acidic system when the system is basic to combine the decomposed polymer and the trifunctional molecule, thereby introducing the alkoxysilyl group into the main chain. Furthermore, acido-basic properties of a system containing a polymer obtained by decomposing by oxidative cleavage of a carbon-carbon double bond to decrease the molecular weight, and a functional molecule having an alkoxysilyl group as represented by the formula (a) are changed in the same manner as above to combine the decomposed polymer and the functional molecule, thereby introducing the alkoxysilyl group in a molecular terminal. ##STR00001##