Raft polymerisation

A method of preparing polymer, the method comprising polymerising one or more ethylenically unsaturated monomers of formula (IV)

• where W is H or forms together with V1 a lactone, anhydride or imide ring;
• U1 is selected from H, C1-C4 alkyl, CO2R1 and halogen;
• V1 forms together with W a lactone, anhydride or imide ring, or is selected from optionally substituted aryl, alkenyl, CO2H, CO2R1, COR1, CN, CONH2, CONHR1, CONR12, PO(OR1)2, PO(R1)2, PO(OH)R1, PO(OH)2, SO(OR1), SO2(OR1), SOR1 and SO2R1;
• and where the or each R1 is independently selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted alkylaryl, optionally substituted alkylheteroaryl, and an optionally substituted polymer chain,
• under the control of a RAFT agent Lewis adduct of formula (V) or (VI),
• where Y is a Lewis base moiety;
• Y* is an (n+1)-valent Lewis base moiety;
• X is O or NR1, R1 forms together with Y and N a heterocyclic ring, or R1 is independently selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted alkylaryl, optionally substituted alkylheteroaryl, and an optionally substituted polymer chain;
• m is an integer ≧1;
• n is an integer ≧2;
• A is a Lewis acid moiety associated with Y or Y* forming the respective adducts;
• R* is a m-valent radical leaving group that affords R*. which initiates free radical polymerisation of the one or more ethylenically unsaturated monomers of formula (IV), and where R is a free radical leaving group that affords R. which initiates free radical polymerisation of the one or more ethylenically unsaturated monomers of formula (IV).

A method of preparing polymer, the method comprising:

• polymerising one or more ethylenically unsaturated monomers of formula (IV)
• where W is H or forms together with V1 a lactone, anhydride or imide ring;
• U1 is selected from H, C1-C4 alkyl, CO2R1 and halogen;
• V1 forms together with W a lactone, anhydride or imide ring or is selected from optionally substituted aryl, alkenyl, CO2H, CO2R1, COR1, CN, CONH2, CONHR1, CONR12, PO(OR1)2, PO(R1)2, PO(OH)R1, PO(OH)2, SO(OR1), SO2(OR1), SOR1 and SO2R1;
• and where the or each R1 is independently selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted alkylaryl, optionally substituted alkylheteroaryl, and an optionally substituted polymer chain,
• under the control of a RAFT agent Lewis adduct of formula (V) or (VI),
• where Y is a Lewis base moiety and Y* is an (n+1)-valent Lewis base moiety;
• X is O or NR1, R1 is as defined above or forms together with Y and N a heterocyclic ring;
• m is an integer ≧1;
• n is an integer ≧2;
• A is a Lewis acid moiety associated with Y or Y* forming the respective adducts;
• R* is a m-valent radical leaving group that affords R*. which initiates free radical polymerisation of the one or more ethylenically unsaturated monomers of formula (IV);
• and where R is a free radical leaving group that affords R. which initiates free radical polymerisation of the one or more ethylenically unsaturated monomers of formula (IV),
• to form a macro-RAFT agent Lewis adduct;
• (ii) disassociating A from Y or Y* in the so formed macro-RAFT agent Lewis adduct to thereby form a macro-RAFT agent;
• and
• (iii) polymerising one or more ethylenically unsaturated monomers of formula (I)
• where U is selected from H, C1-C4 alkyl or halogen;
• V is halogen or of the form O-G where G is selected from —C(O)R1 and —R1, or V is of the form NGGa where G is as defined above and Ga is selected from H and R1, or G and Ga form together with N a heterocyclic ring, or V is of the form CH2Gb where Gb is selected from H, R1, OH, OR1, NR12, PR12, P(O)R12, P(OR1)2, SR1, SOR1, and SO2R1;
• and where the or each R1 is independently selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted alkylaryl, optionally substituted alkylheteroaryl, and an optionally substituted polymer chain,
• under the control of the macro-RAFT formed in step (ii).

A RAFT agent or RAFT agent precursor of formula (XI)-(XIV),

• where X is O or NR1, R1 is independently selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted alkylaryl, optionally substituted alkylheteroaryl, and an optionally substituted polymer chain;
• R* is a m-valent radical leaving group that affords R*. which initiates free radical polymerisation of one or more ethylenically unsaturated monomers, or m in formula (XI) and (XII) is 1 and then R* in formula (XI) is —S—(C═S)—X—Ya or in formula (XIII) is —S—(C═S)—X—Ya—A;
• R is a free radical leaving group that affords R. which initiates free radical polymerisation of one or more ethylenically unsaturated monomers, or R in formula (XII) is —S—(C═S)—X—Ya or in formula (XIV) is —S—(C═S)—X—Ya—A;
• m is an integer ≧1;
• n is an integer ≧2;
• A is a Lewis acid moiety associated with Ya or aY* forming the respective adducts of formula (XIII) and (XIV);
• and where Ya is a Lewis base moiety and aY* is an n-valent Lewis base moiety that are each independently selected from optionally substituted heteroaryl and optionally substituted aryl-Q, where Q=NR1R1, PR1R1 and SeR1, and the or each R1 is independently as defined above.

A polymer comprising a moiety of formula (VII) or (VIII)

• where Y is a Lewis base moiety;
• X is O or NR1, R1 forms together with Y and N a heterocyclic ring, or R1 is independently selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted alkylaryl, optionally substituted alkylheteroaryl, and an optionally substituted polymer chain;
• A is a Lewis acid moiety associated with Y forming a Lewis adduct;
• POL is a polymerised residue of one or more ethylenically unsaturated monomers.

A polymer comprising a moiety of formula (VIIa) or (VIIIa)

• where Y is a Lewis base moiety;
• X is O or NR1, R1 forms together with Y and N a heterocyclic ring, or R1 is independently selected from optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted arylalkyl, optionally substituted heteroarylalkyl, optionally substituted alkylaryl, optionally substituted alkylheteroaryl, and an optionally substituted polymer chain;
• A is a Lewis acid moiety associated with Y forming a Lewis adduct;
• PB is a polymerised residue of one or more ethylenically unsaturated monomers of formula (I);
• PD is a polymerised residue of one or more ethylenically unsaturated monomers of formula (IV);
• PR is a polymerised residue of a monomer mixture formed from one or more ethylenically unsaturated monomers of formula (I) and one or more ethylenically unsaturated monomers of formula (IV);
• and where each w is independently 0 or 1;
• where U is selected from H, C1-C4 alkyl or halogen;
• V is halogen or of the form O-G where G is selected from —C(O)R1 and —R1, or V is of the form NGGa where G is as defined above and Ga is selected from H and R1, or G and Ga form together with N a heterocyclic ring, or V is of the form CH2Gb where Gb is selected from H, R1, OH, OR % NR12, PR12, P(O)R12, P(OR1)2, SR % SOR1, and SO2R1;
• and where the or each R1 is as defined above;
• where W is H or forms together with V1 a lactone, anhydride or imide ring;
• U1 is selected from H, C1-C4 alkyl, CO2R1 and halogen;
• V1 forms together with W a lactone, anhydride or imide ring or is selected from optionally substituted aryl, alkenyl, CO2H, CO2R1, COR1, CN, CONH2, CONHR1, CONR12, PO(OR1)2, PO(R1)2, PO(OH)R1, PO(OH)2, SO(OR1), SO2(OR1), SOR1 and SO2R1;
• and where the or each R1 is as defined above.