Atom or group transfer radical polymerization

A (co)polymer selected from the group consisting of water-soluble, water-miscible, water-swellable, and water-dispersible (co)polymers, comprising a molecular weight distribution in one or more segments of less than 2, the (co)polymer having a general formula selected from the group consisting of:

• A—{(M1)p}—X,
• A—{(M1)i(M2)j}—X,
• A—{(M1)i(M2)j(M3)k}—X,
• A—{(M1)i(M2)j(M3)k . . . (Mu)α}—X,
• A—(M1)p—(M2)p—X,
• A—(M1)p—(M2)p—(M3)p—X,
• A—(M1)p—(M2)p—(M3)p— . . . —(Mu)p—X,
• X—M1p—(A′)—M1p—X,
• X—{(M1)i(M2)j}—(A′)—{(M1)i(M2)j}—X,
• X—{(M1)i(M2)j(M3)k}—(A′)—{(M1)i(M2)j(M3)k}—X,
• X—{(M1)i(M2)j(M3)k . . . (Mu)α}—(A′){(M1)i(M2)j(M1)k . . . (Mu)α}—X,
• X—(M2)p—(M1)p—(A′)—(M1)p—(M2)p—X,
• X—(M3)p—(M2)p—(M1)p—(A′)—(M1)p—(M2)p—(M3)p—X,
• X—(Mu)p— . . . —(M3)p—(M2)p—(M1)p—(A′)—(M1)p—(M2)p—(M3)p— . . . —(Mu)p—X,
• A′—{(M1)p—X}z,
• A′—({(M1)i(M2)j}—X)z,
• A′—({(M1)i(M2)j(M3)k}—X)z,
• A′—({(M1)i(M2)j(M3)k . . . (Mu)α}—X)z,
• A′—{(M1)p—(M2)p—X}z,
• A′—{(M1)p—(M2)p—(M3)p—X}z, and
• A′—{(M1)p—(M2)p—(M3)p— . . . —(Mu)p—X}z
• wherein X is a radically transferable atom or a radically transferable group, a halogen, Cl, Br, I, OR10, SR14, SeR14, OC(═O)R14, OP(═O)R14, OP(═O)(OR14)2, O—(R14)2, S—C(═S)N(R14)2, CN, NC, SCN, CNS, OCN, CNO, N3, OH, O, C1-C6-alkoxy, (SO4), PO4, HPO4, H2PO4, triflate, hexafluorophosphate, methanesulfonate, arylsulfonate, carboxylic acid halide, R15CO2, H, NH2, COOH, or CONH2, where R14 is aryl or a straight or branched C1-C20 alkyl group or where an N(R14)2 group is present, the two R14 groups may be joined to form a 5-, 6- or 7-member heterocyclic ring, R15 is H or a straight or branched C1-C6 alkyl group, aryl or aryl substituted 1 to 5 times with a halogen, and R10 is an alkyl of from 1 to 20 carbon atoms or an alkyl of from 1 to 20 carbon atoms in which each of the hydrogen atoms may be replaced by a halide, alkenyl of from 2 to 20 carbon atoms, alkynyl of from 2 to 10 carbon atoms, phenyl, phenyl substituted with from 1 to 5 halogen atoms or alkyl groups with from 1 to 4 carbon atoms, aralkyl, aryl, aryl substituted alkyl, in which the aryl group is phenyl or substituted phenyl and the alkyl group is from 1 to 6 carbon atoms;
• A is a residue of an initiator;
• A′ is a residue of an multifunctional initiator, wherein z is 3 or more, wherein the initiator is of the formula:
• R11C(═O)—X;
• R11R12R13Si—X;
• R11R12N—X;
• R11N—X2;
• (R11)nP(O)m—X3−n;
• or
• (R11)(R12O)P(O)m—X
• where:
• R11, R12 and R13 are each independently selected from the group consisting of H, halogen, C1-C20 alkyl, C3-C8 cycloalkyl, R83Si, C(═Y)R5, C(═Y)NR6R7, COCl, OH, CN, C2-C20 alkenyl or alkynyl, oxiranyl, glycidyl, C2-C6 alkylene or alkenylene substituted with oxiranyl or glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl, aryl-substituted alkenyl, and alkenyl is vinyl which may be substituted with one or two C1-C6 alkyl groups and/or halogen atoms, C1-C6 alkyl in which from 1 to all of the hydrogen atoms are replaced with halogen and C1-C6 alkyl substituted with from 1 to 3 substituents selected from the group consisting of C1-C4 alkoxy, aryl, heterocyclyl, C(═Y)R5, C(═Y)NR6R7, oxiranyl and glycidyl, with the provisio that no more than 2 of R11, R12 and R13 are H;
• R5 is C1-20 alkyl group, C1-20 alkylthio group, OR24, wherein R24 is H or an alkali metal, C1-C20 alkoxy group, aryl, aralkyl, heterocyclyl, aryloxy or heterocyclyloxy,
• R6 and R7 are each independently H or C1-20 alkyl group, or R6 and R7 may be joined together to form a C2-7 alkylene group, thus forming a 3- to 8-membered ring, and
• R8 is H, straight or branched C1-C20 alkyl or aryl;
• with the proviso that when R11 is directly bonded to S or O, R8 may be an alkali metal or an ammonium group;
• m is 0 or 1;
• and
• n is 0, 1 or 2;
• M1, M2, M3, . . . up to Muindependently each represent amonomer unit derived from a radically (co)polymerizable monomer wherein any adjacent blocks are not identical but wherein non-adjacent blocks may be identical, and wherein at least one of the radically (co)polymerizable monomers has the formula:
• wherein R1and R2 are independently selected from the group consisting of H, halogen, CN, aryl, straight or branched C1-10 alkyl group which may be substituted, unsaturated straight or branched alkenyl or alkynyl having 2 to 10 carbon atoms which may be substituted, C3-C8 cycloalkyl which may be substituted, heterocyclyl wherein each H atom may be replaced with halogen atoms or C1-C6 alkyl or alkoxy groups and in which one or more optionally present nitrogen atoms may be quaternized with H or C1-C4 alkyl, NR82, N+R83, COOR9, wherein R9 is H, an alkali metal, or a C1-C20 alkyl group, C(═Y)R5, C(═Y)NR6R7, YC(═Y)R8, YS(═Y)2R8, YS(═Y)2YR8, P(YR8)2,P(═Y)(YR8)2 and P(═Y)R52, wherein Y may be NR9, S or O wherein
• R3 and R4 are independently selected from the group consisting of H, halogen, CN, C1-C6 alkyl and COOR9;
• or
• R1 and R3 may be joined to form a group of the formula (CH2)n′ which may be substituted or a group of the formula C(═O)—Y—C(═O), where n′ is from 2 to 6 and Y is as defined above;
• and
• wherein at least two of R1, R2, R3, and R4 are H or halogen and wherein at least one of R1, R2, R3, and R4 is or is substituted with heterocyclyl having one or more nitrogen atoms quaternized with H or C1-C4 alkyl, NR82, N+R83, COOR9, C(═Y)R5, C(═Y)NR6R7, YC(═Y)R8, YS(═Y)R8,YS(═Y)2R8, YS(═Y)2YR8, P(YR8)2 or P(═Y)R82, or hydroxy-substituted C1-C10 alkyl;
• each i, j, k . . . and a individually represents an average molar ratio of monomer units in the blocks M1, M2, M3, . . . up to Mu to the total number of moles of monomer units in the copolymer or an individual branch of the copolymer;
• and
• p is an average degree of polymerization for each block and is independently selected for each block such that either the average degree of polymerization of each (co)polymer or a block thereof is at least 3 or the number average molecular weight of each (co)polymer or block thereof is at least 250 g/mol.

A gradient copolymer of the formula:

• A—M1p—(M1aM2b)1— . . . —(M1aM2b)y—M2p—X,
• wherein X is a radically transferable atom or a radically transferable group, a halogen, Cl, Br, I, OR10, SR14, SeR14, OC(═O)R14, OP(═O)R14, OP(═O)(OR14)2, O—N(R14)2, S—C(═S)N(R14)2, CN, NC, SCN, CNS, OCN, CNO, N3, OH, O, C1-C6-alkoxy, (SO4), PO4, HPO4, H2PO4, triflate, hexafluorophosphate, methanesulfonate, arylsulfonate, carboxylic acid halide, R15CO2, H, NH2, COOH, or CONH2, where R14 is aryl or a straight or branched C1-C20 alkyl group or where an N(R14)2 group is present, the two R14 groups may be joined to form a 5-, 6- or 7-member heterocyclic ring, R15 is H or a straight or branched C1-C6 alkyl group, aryl or aryl substituted 1 to 5 times with a halogen, and R10 is an alkyl of from 1 to 20 carbon atoms or an alkyl of from 1 to 20 carbon atoms in which each of the hydrogen atoms may be replaced by a halide, alkenyl of from 2 to 20 carbon atoms, alkynyl of from 2 to 10 carbon atoms, phenyl, phenyl substituted with from 1 to 5 halogen atoms or alkyl groups with from 1 to 4 carbon atoms, aralkyl, aryl, aryl substituted alkyl, in which the aryl group is phenyl or substituted phenyl and the alkyl group is from 1 to 6 carbon atoms;
• A is a residues of an initiator;
• wherein the initiator is of the formula:
• R11C(═O)—X;
• R11R12R13Si—X;
• R11R12N—X;
• R11N—X2;
• (R11)nP(O)m—X3−n;
• or
• (R11)(R12O)P(O)m—X
• where:
• R11, R12 and R13 are each independently selected from the group consisting of H, halogen, C1-C20 alkyl, C3-C8 cycloalkyl, R83Si, C(═Y)R5, C(═Y)NR6R7, COCl, OH, CN, C2-C20 alkenyl or alkynyl, oxiranyl, glycidyl, C2-C6 alkylene or alkenylene substituted with oxiranyl or glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl, aryl-substituted alkenyl, and alkenyl is vinyl which may be substituted with one or two C1-C6 alkyl groups and/or halogen atoms, C1-C6 alkyl in which from 1 to all of the hydrogen atoms are replaced with halogen and C1-C6 alkyl substituted with from 1 to 3 substituents selected from the group consisting of C1-C4 alkoxy, aryl, heterocyclyl, C(═Y)R5, C(═Y)NR6R7, oxiranyl and glycidyl, with the provisio that no more than 2 of R11, R12 and R13 are H;
• R5 is C1-20 alkyl group, C1-20 alkylthio group, OR24 wherein R24 is H or an alkali metal, C1-20alkoxy group, aryl, aralkyl, heterocyclyl, aryloxy or heterocyclyloxy,
• R6 and R7 are each independently H or C1-20 alkyl group, or R6 and R7 may be joined together to form a C2-7 alkylene group, thus forming a 3- to 8-membered ring, and
• R8 is H, straight or branched C1-C20 alkyl or aryl;
• with the proviso that when R8 is directly bonded to S or O, R8 may be an alkali metal or an ammonium group;
• m is 0 or 1;
• and
• n is 0, 1 or 2;
• M1 and M2 each represent monomer units derived from radically (co)polymerizable monomers;
• y is the total number of blocks;
• a is an average molar percentage of M1 in each block determined independently for each block of the copolymer indicated by the parenthesis;
• b is a molar percentage of M2 in each block determined independently for each block of the copolymer indicated by the parenthesis;
• such that a+b=100 percent for each block, and the molar percentage of M1changes for each subsequent block along the length of each polymer chain from the residue of the initiator to the radically transferable atom or group or a group derived therefrom, block y;
• and
• p is an average degree of polymerization of at least 2 selected independently for each monomer unit.

An amphiphilic (co)polymer having a formula selected from the group consisting of:

• A—{(M1)i(M2)j}—X,
• A—{(M1)i(M2)j(M3)k}—X,
• A—{(M1)i(M2)j(M3)k . . . (Mu)α}—X,
• A—(M1)p—(M2)p—X,
• A—(M1)p—(M2)p—(M3)p—X,
• A—(M1)p—(M2)p—(M3)p— . . . —(Mu)p—X,
• A′—({(M1)i(M2)j}—X)z,
• A′—({(M1)i(M2)j(M3)k}—X)z,
• A′—({(M1)i(M2)j)(M3)k . . . (Mu)α}—X)z,
• A′—{(M1)p—(M2)p—X}z,
• A′—{(M1)p—(M2)p—(M3)p—X}z, and
• A′—{(M1)p—(M2)p—(M3)p— . . . —(Mu)p)—X}z
• wherein X is a radically transferable atom or a radically transferable group, a halogen, Cl, Br, I, OR10, SR14, SeR14, OC(═O)R14, OP(═O)R14, OP(═O)(OR14)2, O—(R14)2, S—C(═S)N(R14)2, CN, NC, SCN, CNS, OCN, CNO, N3, OH, O, C1-C6-alkoxy, (SO4), PO4, HPO4, H2PO4, triflate, hexafluorophosphate, methanesulfonate, arylsulfonate, carboxylic acid halide, R15CO2, H, NH2, COOH, or CONH2, where R14 is aryl or a straight or branched C1-C20 alkyl group or where an N(R14)2 group is present, the two R14 groups may be joined to form a 5-, 6- or 7- member heterocyclic ring, R15 is H or a straight or branched C1-C6 alkyl group, aryl or aryl substituted 1 to 5 times with a halogen, and R10 is an alkyl of from 1 to 20 carbon atoms or an alkyl of from 1 to 20 carbon atoms in which each of the hydrogen atoms may be replaced by a halide, alkenyl of from 2 to 20 carbon atoms, alkynyl of from 2 to 10 carbon atoms, phenyl, phenyl substituted with from 1 to 5 halogen atoms or alkyl groups with from 1 to 4 carbon atoms, aralkyl, aryl, aryl substituted alkyl, in which the aryl group is phenyl or substituted phenyl and the alkyl group is from 1 to 6 carbon atoms;
• A is a residue of an initiator;
• A′ is a residue of an multifunctional initiator;
• wherein z is 2 or more, wherein the initiator is of the formula:
• R11C(═O)—X;
• R11R12R13Si—X;
• R11R12N—X;
• R11N—X2;
• (R11)nP(O)m—X3−n;
• or
• (R11)(R12O)P(O)m—X
• where:
• R11, R12 and R13 are each independently selected from the group consisting of H, halogen, C1-C20 alkyl, C3-C8 cycloalkyl, R83Si, C(═Y)R5, C(═Y)NR6R7, COCl, OH, CN, C2-C20 alkenyl or alkynyl, oxiranyl, glycidyl, C2-C6 alkylene or alkenylene substituted with oxiranyl or glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl, aryl-substituted alkenyl, and alkenyl is vinyl which may be substituted with one or two C1-C6 alkyl groups and/or halogen atoms, C1-C6 alkyl in which from 1 to all of the hydrogen atoms are replaced with halogen and C1-C6 alkyl substituted with from 1 to 3 substituents selected from the group consisting of C1-C4 alkoxy, aryl, heterocyclyl, C(═Y)R5, C(═Y)NR6R7, oxiranyl and glycidyl, with the provisio that no more than 2 of R11, R12 and R13 are H;
• m is 0 or 1;
• and
• n is 0, 1 or 2;
• M1, M2, M3, . . . up to Mu independently each represent a monomer unit derived a radically (co)polymerizable monomer, wherein any adjacent blocks are not identical but wherein non-adjacent blocks may be identical, and wherein at least one of the radically (co)polymerizable monomers has the formula:
• wherein R1 and R2 are independently selected from the group consisting of H, halogen, CN, aryl, straight or branched alkyl of from 1 to 10 carbon atoms which may be substituted, unsaturated straight or branched C2-10 alkenyl or alkynyl which may be substituted, C3-C8 cycloalkyl which may be substituted, heterocyclyl in which each H atom may be independently replaced with halogen atoms or C1-C6 alkyl or alkoxy groups and in which one or more nitrogen atoms when present may be quaternized with H or C1-C4 alkyl, NR82, N+R83, COOR9, wherein R9 is H, an alkali metal, or a C1-C20 alkyl group, C(═Y)R5, C(═Y)NR6R7, YC(═Y)R8, YS(═Y)R8, YS(═Y)2YR8, P(YR8)2, P(═Y)(YR8)2 and P(═Y)R52, where Y may be NR9, S or O, wherein
• R5 is C1-20 alkyl, C1-20 alkylthio, OR24 where R24 is H or an alkali metal, C1-20 alkoxy, aryl, aralkyl, heterocyclyl, aryloxy or heterocyclyloxy, group, and
• R6 and R7 are independently H or C1-20 alkyl, or R6 and R7 may be joined together to form a C2-7 alkylene group, thus forming a 3- to 8-membered ring, and
• R8 is H, straight or branched C1-C20 alkyl or aryl;
• with the proviso that wherein when R8 is directly bonded to S or O, R8 may be an alkali metal or an ammonium group;
• and
• R3 and R4 are independently selected from the group consisting of H, halogen, CN, C1-C6 alkyl and COOR9;
• or
• R1 and R3 may be joined to form a group of the formula (CH2)n′ which may be substituted or C(═O)—Y—C(═O), where n′ is from 2 to 6 and Y is as defined above;
• and
• wherein at least two of R1, R2, R3, and R4 are H or halogen and wherein at least one of R1, R2, R3, and R4 is or is substituted with heterocyclyl in which one or more nitrogen atoms is quaternized with H or C1-C4 alkyl, NR82, N+R83, COOR9, C(═Y)R5, C(═Y)NR6R7, YC(═Y)R8, YS(═Y)R8, YS(═Y)2R8, YS(═Y)2YR8, P(YR8)2, P(═Y)(YR8)2 or P(═Y)R82, or hydroxy-substitued C1-C10 alkyl;
• each i, j, k . . . and a independently represents an average molar ratio of the moles of monomer units M1, M2, M3, . . . up to Muto the total number of moles of monomer units in the copolymer or an individual branch of the copolymer;
• and
• p is an average degree of polymerization independently selected for each block wherein either the average degree of polymerization for each block is at least 3 or a number average molecular weight of each block is at least 250 g/mol.

A periodic copolymer of the formula:

• A—{(M1)p(M2)p(M3)p . . . (Mu)p}—X, or
• A′—{(M1)p(M2)p(M3)p . . . (Mu)p—X}z,
• wherein X is a radically transferable atom or a radically transferable group, a halogen, Cl, Br, I, OR10, SR14, SeR14, OC(═O)R14, OP(═O)R14, OP(═O)(OR14)2, O—(R14)2, S—C(═S)N(R14)2, CN, NC, SCN, CNS, OCN, CNO, N3, OH, O, C1-C6-alkoxy, (SO4), PO4, HPO4, H2PO4, triflate, hexafluorophosphate, methanesulfonate, arylsulfonate, carboxylic acid halide, R15CO2, H, NH2, COOH, or CONH2, where R14 is aryl or a straight or branched C1-C20 alkyl group or where an N(R14)2 group is present, the two R14 groups may be joined to form a 5-, 6- or 7- member heterocyclic ring, R15 is H or a straight or branched C1-C6 alkyl group, aryl or aryl substituted 1 to 5 times with a halogen, and R10 is an alkyl of from 1 to 20 carbon atoms or an alkyl of from 1 to 20 carbon atoms in which each of the hydrogen atoms may be replaced by a halide, alkenyl of from 2 to 20 carbon atoms, alkynyl of from 2 to 10 carbon atoms, phenyl, phenyl substituted with from 1 to 5 halogen atoms or alkyl groups with from 1 to 4 carbon atoms, aralkyl, aryl, aryl substituted alkyl, in which the aryl group is phenyl or substituted phenyl and the alkyl group is from 1 to 6 carbon atoms;
• A is a residue of an initiator:
• A′ is a residue of an multifunctional initiator;
• wherein z is 2 or more;
• M1, M2, M3, . . . up to Mu independently each represent a monomer unit derived from a radically (co)polymerizable monomer wherein the monomer units are distributed in a regular sequence along each polymeric chain;
• and
• p is an average mole fraction of each monomeric unit in each polymer chain for each and is independently selected for each monomeric unit such that the (co)polymer or a block thereof has an average degree polymerization of at least 3 or the weight or the number average molecular weight of the (co)polymer or a block thereof at least is 250 g/mol.

A poly-telechelic polymer having a molecular weight distribution of less than 2, comprising:

• monomer units derived from radically (co)polymerizable monomers;
• a terminal hydroxyl group;
• and
• a terminal isocyanate group.