Polymer brushes with chain-ends functionalized with metal coordinating two hetero elements for selective surface modification

A polymer of structure (A), comprising two end groups R3p and R4p, and a polymer chain (R) comprising either a repeat unit of structure (Ip) or a repeat unit of structure (lip), wherein

• end group R3p, which is derived from an anionic initiator, is either a C-1 to C-8 alkyl, a moiety of structure (IIIp), or a moiety of structure (IIIp1), but where R3p can only be selected from a C-1 to C-8 alkyl if the in the polymer chain (R) the repeat unit is (IIp), and further where R3p can only be selected from a moiety of structure (IIIp) or structure (IIIp1) if in the polymer chain (R) the repeat unit is of structure (Ip),
• end group R4p is either a moiety selected from the group consisting of H, a C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(═O)—), a C-1 to C-8 trialkylsilyl ((alkyl)3Si—), a C-1 to C-8 dialkysilyl ((alkyl)2HSi—), a C-1 to C-8 monoalkylsilyl ((alkyl)H2Si—), silane (H3Si—), and a benzylic moiety, a moiety of structure (IVp), a moiety of structure (IVp1) or a moiety of structure (IVp2), further end groups R3p and R3p cannot respectively, both simultaneously be moieties of structure (IIIp) and (IVp), both simultaneously be moieties of structure (IIIp) and (IVp1), or both simultaneously be moieties of structure (IIIp) and (IVp2), but where said polymer of structure (A) must contain one end group moiety selected from structures (IIIp), (IVp), (IVp1) or (IVp2),
• in said repeat unit of structure (Ip) Rm1 is a C-1 to C-8 alkyl, R1, is a C-1 to C-8 alkyl, and n1 is the number of this repeat units in polymer chain (R);
• in said repeat unit of structure (lip) R2 is H or a C-1 to C-8 alkyl, R2p is H or a C-1 to C-8 alkyl, n2 is the number of this repeat unit polymer chain (R);
• and
• in structure (IIIp),
• R1 is a chelating group, located at the para or meta position, selected from a phosphinothioic moiety of structure (Ia) an aminosulfonyl moiety of structure (Ib), a phosphonamide moiety of structure (Ic), where *** designates the attachment point of this end group moiety to the polymer of structure (A), wherein
• in said phosphinothioic moiety of structure (Ia), R3 and R4 are independently an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy;
• and a dialkyl amino moiety, —N(R9)(R10), in which R9 and R10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, and designates the attachment point of this moiety to an end group moiety of structure of (IIIp),
• in said aminosulfonyl moiety of structure (Ib), R5 and R6, are independently a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, and said dialkyl amino moiety, —N(R9)(R10), and designates the attachment point of this moiety to an end group moiety of structure of (IIIp),
• in said phosphonamide moiety of structure (Ic), R7 is said dialkyl amino moiety, —N(R9)(R10), and R8 is selected from the group consisting of an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy or a C-3 to C-8 cyclic alkyloxy, and designates the attachment point of this moiety to an end group moiety of structure of (IIIp),
• R2 is selected from the group consisting of H, an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy;
• a phosphinothioic moiety of structure (Ia), an aminosulfonyl of structure (Ib), and a phosphonamide of structure (Ic), and
• R15 is a C-1 to C-8 alkyl, and Re1 and Re2 are individually selected from H, a C-1 to C-8 alkyl, and a C-1 to C-8 alkoxy,
• in structure (IIIp1),
• Re1 and Re2 are individually selected from H, an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy, and R15 is a C-1 to C-8 alkyl, and ** designates the attachment point of this end group moiety to the polymer of structure (A),
• in structure (IVp),
• R12 is H or a C-1 to C-4 alkyl,
• R11 is a phosphinothioic moiety of structure (IIa), wherein designates the attachment point of this phosphinothioic moiety to structure (IVp), wherein
• R13 and R14 are independently selected from the group consisting of an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy;
• and a dialkyl amino moiety, —N(R9)(R10), in which Rs and R10 are independently selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl,
• L1 is a linking moiety selected from the group consisting of a direct valence bond, a C-2 to C-8 alkylene moiety(-alkylene-), an arylene moiety (-aryl-), an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), an alkylenearyl moiety (*-alkylene-aryl-**), wherein * designates the attachment points of the L1 organic linking moiety to the phosphorous in structure (IIa), and * designates where L1 within the moiety R11 is attached to carbonyloxy of structure (IVp),
• R17 is selected from the group consisting of H, a C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(═O)—), a C-1 to C-8 trialkylsilyl ((alkyl)3Si—), a C-1 to C-8 dialkysilyl ((alkyl)2HSi—), a C-1 to C-8 monoalkylsilyl ((alkyl)H2Si—), silane (H3Si—), and a benzylic moiety, and ** designates the attachment point of this end group moiety to the polymer of structure (A),
• in structure (IVp1),
• L is either a direct valence bond or a linking group selected from a C-1 to C-8 linear alkylene, C-3 to C-8 branched alkylene, and a C-5 to C-8 cyclic alkylene, an alkyleneoxyaryl moiety (*-alkylene-O-aryl-**), and an alkylenearyl moiety (*-alkylene-aryl-**), wherein * designates the attachment points of the L linking moiety to the phosphorous in structure (IVp1), and * designates where L is attached to said polymer of structure (A), and Rs and Rs1 are individually selected from a C-1 to C-8 alkoxy or a C-1 to C-8 alkyl, and where ** designates the attachment point of this end group moiety to the polymer of structure (A),
• in structure (IVp2),
• R1 is a chelating group, located at the para or meta position, selected from said phosphinothioic moiety of structure (Ia) said aminosulfonyl moiety of structure (Ib), and said phosphonamide moiety of structure (Ic),
• R2 is selected from the group consisting of H, an aryl, an alkylenearyl, a C-2 to C-8 alkyleneoxyalkyl, a C-2 to C-8 haloalkyl, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl, a C-3 to C-8 cyclic alkyl, a C-1 to C-8 linear alkyloxy, a C-3 to C-8 branched alkyloxy, a C-3 to C-8 cyclic alkyloxy;
• a phosphinothioic moiety of structure (Ia), an aminosulfonyl of structure (Ib), and a phosphonamide of structure (Ic), R18 is selected from the group consisting of H, a C-1 to C-8 alkyl, C-1 to C-8 alkylcarbonyl (alkyl-C(═O)—), a C-1 to C-8 trialkylsilyl ((alkyl)3Si—), a C-1 to C-8 dialkysilyl ((alkyl)2HSi—), a C-1 to C-8 monoalkylsilyl ((alkyl)H2Si—), silane (H3Si—), and a benzylic moiety,
• and where *** designates the attachment point of this end group moiety to the polymer of structure (A),
• Further, said polymer of structure (A) has a Mn ranging from about 4000 to about 7000, and has a polydispersity ranging from 1 to about 1.15;