Non-thiol nitrogen based hydrophobic polymer brush materials and use thereof for modification of substrate surfaces

A functional polymer comprising either acrylic repeat units, styrenic repeat units or a mixture of these having a polydispersity from 1 to about 1.12 comprising at least one reactive moiety selected from the group consisting of

• a moiety comprising at least one N-coordinative functional group having at least one lone pair of electrons, a moiety comprising a dialkylsilyl group, and a mixture of both groups, wherein said reactive moiety is present in said functional polymer either on a repeat unit, on an end group or on both, and
• said N-coordinative functional group is either a monodentate N-coordinative functional group, a polydendate N-coordinative group or a mixture thereof, and
• said monodentate N-coordinative functional group is an azide moiety (—N3), or a cyano moiety (—CN), and said polydendate N-coordinative functional group is either a moiety comprising 2 or 3 monocyclic heteroaryl moieties, wherein each said heteroaryl individually contains 1 to 3 nitrogen hetero atoms, or a polycyclic fused ring heteroaryl moiety containing 2 to 4 nitrogen heteroatoms,
• where further said functional polymer is selected from the group consisting of a functional polymer having structure (I),
• wherein n is the number of repeating units in the polymer;
• R1 is H or a C-1 to C-4 linear alkyl;
• R2 is selected from a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• Rs is selected from the group consisting of H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• R3 is selected from the group consisting of H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• and a dialkylsilyl moiety [(Rsi)(Rsia) SiH—] wherein Rsi and Rsia are independently selected from the group consisting of a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• and X and Xa are independently selected from the group consisting of a direct valence bond, a C-1 to C-8 linear alkylene moiety, a C-3 to C-8 branched alkylene moiety, a C-3 to C-8 cyclic alkylene moiety, and a —X1—O—X2— (-alkyleneoxyalkylene-) moiety wherein X1 and X2 are independently selected from the group consisting of a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene and a C-3 to C-8 cyclic alkylene;
• and MDN is an azide moiety (—N3), or a cyano moiety (—CN),
• a functional polymer having structure (II),
• wherein na is the number of repeating units in the polymer;
• R1a is H or a C-1 to C-4 linear alkyl;
• Rs is selected from the group consisting of H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• R2a is selected from the group consisting of a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• Xb is selected from the group consisting of a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene, a C-3 to C-8 cyclic alkylene and a —X1a—O—X2a— (-alkyleneoxyalkylene-) moiety wherein X1a and X2a are independently selected from the group consisting of a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene and a C-3 to C-8 cyclic alkylene;
• MDN is an azide moiety (—N3), or a cyano moiety (CN),
• a functional polymer having structure (III),
• wherein, nb is the number of repeating units in the polymer;
• R1b is H or a C-1 to C-4 linear alkyl;
• Rs is selected from the group consisting of H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• R2b is selected from the group consisting of a C-1 to C-8 linear alkyl a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• Xc is selected from the group consisting of a direct valence bond, a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene, a C-3 to C-8 cyclic alkylene, and a —X1b—O—X2b— (-alkyleneoxyalkylene-) moiety wherein X1b and X2b are independently selected from the group consisting of a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene and a C-3 to C-8 cyclic alkylene;
• R4 is a polydentate N-coordinative functional group having a structure selected from the group consisting of moieties IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), and (IIIk), wherein * designate the attachment point of these polydentate moieties to structure (III),
• a functional polymer which is a diblock copolymer having structure (IV),
• wherein nc is the number of repeating units in a first block and nd is the number of repeat units in a second block;
• R1c is H or a C-1 to C-4 linear alkyl;
• Rs is selected from the group consisting of H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• R2c is selected from the group consisting of a C-1 to C-8 linear alkyl a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• Xd and Xe are independently selected from the group consisting of a direct valence bond, a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene, a C-3 to C-8 cyclic alkylene, and a —X1c—O—X2c— (-alkyleneoxyalkylene-) moiety wherein X1c and X2c are independently selected from the group consisting of a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene and a C-3 to C-8 cyclic alkylene;
• R3a is selected from the group consisting of H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl a C-1 to C-8 cyclic alkyl and a dialkylsilyl moiety [(Rsib)(Rsic) SiH—] wherein Rsib and Rsic are independently selected from the group consisting of a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• and MDN is an azide moiety (—N3), or cyano moiety (—CN);
• a functional polymer which is a diblock having structure (V),
• wherein ne is the number of repeating units in a first block and nf is the number of repeat units in a second block;
• R1d is H or a C-1 to C-4 linear alkyl;
• Rs is selected from the group consisting of H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• R2d is selected from the group consisting of a C-1 to C-8 linear alkyl a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• Xf and Xg are independently selected from the group consisting of a direct valence bond, a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene, a C-3 to C-8 cyclic alkylene, and a —X1d—O—X2d— (-alkyleneoxyalkylene-) moiety wherein X1d and X2d are independently selected from the group consisting of a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene, and a C-3 to C-8 cyclic alkylene;
• R5 is a polydentate N-coordinative functional having a structure selected from the group consisting of moieties (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg), (IIIh), (IIIi), (IIIj), and (IIIk), wherein * designate the attachment point of these polydentate moieties to structure (V);
• and MDN is an azide moiety (—N3), or a cyano moiety (—CN),
• and a functional polymer having structure (VIII),
• where, nh is the number of repeating units in the polymer;
• R1f is H or a C-1 to C-4 linear alkyl;
• Rs is selected from the group consisting of H, a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• R2f is selected from the group consisting of a C-1 to C-8 linear alkyl a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl;
• Xe is selected from the group consisting of a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene, a C-3 to C-8 cyclic alkylene, and a —X1f—O—X2f— (-alkyleneoxyalkylene-) moiety wherein X1f and X2f are independently selected from the group consisting of a C-1 to C-8 linear alkylene, a C-3 to C-8 branched alkylene and a C-3 to C-8 cyclic alkylene;
• R7 and R8 are independently selected from the group consisting of a C-1 to C-8 linear alkyl, a C-3 to C-8 branched alkyl and a C-3 to C-8 cyclic alkyl.