(Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization

A block copolymer, comprising:

• at least two units obtained from one or more radically (co)polymerizable monomers, wherein each unit is substantially similar in microstructure and length such that the molecular weight distribution is less than 2;
• and
• a residue from an initiator in the copolymer connecting the units;
• and
• a member selected from the group consisting of radically transferable atoms, radically transferable groups, halogen, Cl, Br, I, OH, CN, N3, OR10, SR14, SeR14, OC(═O)R14, OP(═O)R14, OP(═O)(OR14)2, O—N(R14)2, carboxylic acid halide, H, NH2, COOH, and olefinic end groups, 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, 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 attached to the units.

A (co)polymer, exhibiting a stereochemistry and microstructure, as defined by tacticity and sequence distribution, of a polymer formed by a free radical polymerization process and displaying a molecular weight distribution of less than 2.0 and calculable number average molecular weight, having the formula:

• R11R12R13C—(M1)p—X,
• R11R12R13C—(M1)p—(M2)p—X,
• R11R12R13C—(M1)p—(M2)p—(M3)p—X,
• or
• R11R12R13C—(M1)p—(M2)p—(M3)p— . . . —(Mt)p—X
• wherein X is selected from the group consisting of Cl, Br, I, OR10, SR14, SeR14, O—N(R14)2, S—C(═S)N(R14)2, H, OH, N3, NH2, COOH, CONH2, halogen, OC(═O)R14, OP(═O)R14, OP(═O)(OR14)2, carboxylic acid halide, and olefinic end groups, 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, 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 , where
• R10 is an alkyl of from 1 to 20 carbon atoms in which each of the hydrogen atoms may be independently replaced by halide, R14 is aryl or a straight or branched C1-C20 alkyl group, and where an N(R14)2 group is present, the two R14 groups may be joined to form a 5- or 6-membered heterocyclic ring,
• R11, R12 and R13 are each independently selected from the group consisting of H, halogen, C1-C20 alkyl, C3-C8 cycloalkyl, C(═Y)R5, C(═Y)NR6R7, COCl, OH, CN, C2-C20 alkenyl, C2-C20 alkynyl oxiranyl, glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl, 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,
• where Y is NR8, S or O;
• where R5 is an aryl or an alkyl of from 1 to 20 carbon atoms, alkoxy of from 1 to 20 carbon atoms, aryloxy or heterocyclyloxy;
• and R6 and R7 are independently H or alkyl of from 1 to 20 carbon atoms, or R6 and R7 may be joined together to form an alkylene group of from 2 to 5 carbon atoms, thus forming a 3- to 6-membered ring, such that no more than two of R11, R12 and R13 are H, and R8 is H, a straight or branched C1-C20 alkyl or aryl, and
• M1, M2, M3, . . . up to Mt are each monomer units derived from radically (co)polymerizable monomer selected such that the monomers units in adjacent blocks are not identical, and t is an integer greater than 3;
• p is an average degree of polymerization for each block is independently selected such that the number average molecular weight of each block is up to 250,000 g/mol;
• the following formulas:
• X—(M1)p—(R12R13C)—(R11)—(M1)p—X,
• X—(M2)p—(M1)p—(R12R13C)—(R11)—(M1)p—(M2)p—X,
• X—(M3)p—(M2)p—(M1)p—(R12R13C)—(R11)—(M1)p—(M2)p—(M3)p—X,
• or
• X—(Mt)p— . . . —(M3)p—(M2)p—(M1)p—(R12R13C)—(R11)—(M1)p—(M2)p—(M3)p— . . . —(Mt)p—X
• wherein R11, R12, R13, X, M1, M2, M3, . . . up to Mt, t, and p are as defined above, with the provisio that R11 has a polymer chain as indicated attached thereto;
• of the formulas:
• (R11′R12′R13′C)—{(M1)p—X},
• (R11′R12′R13′C)—{(M1)p—(M2)p—X},
• (R11′R12′R13′C)—{(M1)p—(M2)p—(M3)p—X},
• or
• (R11′R12′R13′C)—{(M1)p—(M2)p—(M3)p— . . . —(Mt)p—X}
• wherein {(M1)p—X}, {(M1)p—(M2)p—X}, {(M1)p—(M2)p—(M3)p—X}, and {(M1)p—(M2)p—(M3)p— . . . —(Mt)p—X} are polymer chains, R11′, R12′ and R13′ are the same as R11, R12 and R13 as previously defined with the proviso that R11′, R12′ and R13′ together comprise an additional 2 to 5 of the polymer chains, where X is as defined above;
• M1, M2, M3, . . . Mt, p, and t are as defined above;
• and
• and copolymers comprising a block or graft with the above composition;
• and of the formula:
• R11R12R13C—(M1aM2b)—(M1cM2d)—(M1eM2f)— . . . —(M1αM2β)—(M1γM2δ)—X,
• or
• R11′R12′R13′C—{(M1aM2b)—(M1cM2d)—(M1eM2f)— . . . —(M1αM2β)—(M1γM2δ)—X}
• wherein {(M1aM2b)—(M1cM2d)—(M1eM2f)— . . . —(M1αM2β)—(M1γM2δ)—X} is a polymer chain, R11, R12, R13 are as defined above, M1 and M2 are as defined above and where R11′, R12′ and R13′ are the same as R11, R12 and R13 with the proviso that R11′, R12′ and R13′ together comprise an additional 1 to 5 of the polymer chains, and
• a, b, c, d, e, f, α, β,γ, δ and such parameters for any intervening blocks are molar percentages of monomer in each block and are independently selected such that a+b=c+d=100%, and any or all of (e+f), (α+β) and (γ+δ)=100% or 0, wherein the a:b ratio is from 100:0 to 0:100, the c:d ratio is from 95:5 to 5:95, such that c<a and d>b, and where applicable, the e:f ratio is from 90:10 to 10:90, such that e<c and f>d, and the endpoints of the molar ratio ranges of first monomer to second monomer in successive blocks progressively decrease or increase such that the e:f ratio is from 5:95 to 95:5, such that e≠c and f≠d, and the γ:δ ratio is from 0:100 to 100:0, such that γ≠e and δ≠f.

A polymer, comprising:

• one or more free radically (co)polymerizable monomers, wherein the (co)polymer exhibits a stereochemistry and microstructure, as defined by tacticity and sequence distribution, of a material formed by a free radical polymerization process;
• a molecular weight distribution of less than 2.0;
• residues of a polymerization initiator at each polymer end;
• and
• a number average molecular weight in excess 20,000 g/mol.

A block copolymer, comprising:

• at least two units obtained from one or more radically (co)polymerizable monomers, wherein each unit is substantially similar in microstructure and similar in microstructure and length such that the molecular weight distribution is less than 2;
• and
• a residue from an initiator in the copolymer;
• and
• a radically transferable atom or group at each polymer chain end, wherein the block copolymer is a poly(styrene-block-acrylate-block-styrene) copolymer having a radically transferable atom or group at each polymer chain end.

A polymer of the formula:

• R11R12R13C—(M1)p—X,
• X—(M1)p—R11R12C—(M1)p—X
• R11′R12′R13′C—{(M1)p—X}
• wherein {(M1)p—X} is a polymer chain where M1 is a radically polymerizable monomer and each p is an average degree of polymerization for each block and is independently selected such that the number average molecular weight of the polymer is up to 1,000,000 g/mol,
• X is selected from the group consisting of Cl, Br, I, OR10, SR14, O—N(R14)2, S—C(═S)N(R14)z, H, OH, N3, NH2, COOH and CONH2, where
• R10 is an aryl or an alkyl of from 1 to 20 carbon atoms in which each of the hydrogen atoms may be independently replaced by halide, R14 is aryl or a straight or branched C1-C20, alkyl group, and where an N(R14)2 group is present, the two R14 groups may be joined to form a 5- or 6-membered heterocyclic ring,
• R11, R12 and R13 are each independently selected from the group consisting of H, halogen, C1-C20 alkyl, C3-C8 cycloalkyl, C(═Y)R5, C(═Y)R5, C(═Y)NR6R7, COC1, OH, CN, C2-C20 alkenyl, C2-C20 alkynyl oxiranyl, glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl, 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, where Y is NR8,S or O;
• R8 is H, straight or branched C1-C20 alkyl or aryl;
• R11′, R12′ and R13′ are the same as R11, R12 and R13 with the proviso that R11′, R12′ and R13′ together comprise an additional 2 to 5 of the polymer chains;
• R5 is aryl, alkyl of from 1 to 20 carbon atoms, alkoxy of from 1 to 20 carbon atoms, aryloxy or heterocyclyloxy;
• and R6 and R7 are independently H or alkyl of from 1 to 20 carbon atoms, or R6 and R7 may be joined together to form an alkylene group of from 2 to 5 carbon atoms, thus forming a 3- to 6-membered ring,
• such that no more than two of R11, R12 and R13 are H, and,
• the polymer exhibits a stereochemistry characteristic of a free radical polymerized material in conjunction with a molecular weight distribution of less than 2.0.