Tunable high-chi diblock copolymers consisting of alternating copolymer segments for directed self-assembly and application thereof

A block copolymer comprising structure (1)

• (A)-(C)-(B) (1);
• wherein (A) is a first polymer block segment comprising a copolymer block segment selected from structure (1a), structure (1b), and a mixture of structures (1a) and (1b), wherein Ar, Ara, Arb and Are are each independently selected from the group consisting of unsubstituted aryl moieties or aryl moieties with at least one substituent selected from the group consisting of a C-1 to C-8 alkyl, and moieties comprising a C-5 to C-18 perfluoroalkyl with at least one ether linkage, x, x1, x2 and x3 and x4 are independently the number of repeat units;
• wherein the structures (1a1), (1a2) and (1a3), which are present in structure (1a), structure (1b) or a mixture of structures (1a) and (1b), are present in amounts such that the mole % of structure (1a1) ranges from about 3 mole % to about 40 mole %, as measured against to sum of structures (1a1), (1a2) and (1a3);
• and,
• wherein the Mw of (A) ranges from about 5,000 to about 100,000 g/mole,
• wherein (C) is a spacer moiety comprising structure (1c), wherein Arc and Ard are independently unsubstituted aryl moieties or aryl moieties with at least one substituent selected from the group consisting of a C-1 to C-8 alkyl, and a moiety comprising a C-5 to C-18 perfluoroalkyl with at least one ether linkage,
• wherein (B) is a second polymer block segment comprising repeat units derived from either an alkyl 2-methylenealkanoate (alkyl-O—(C═O)—C(alkyl)=CH2), a lactone, a cyclic carbonate, an oxirane, or an oxetane, wherein the Mw of (B) ranges from about 5,000 g/mol to about 100,000 g/mol;
• and
• said block copolymer comprising structure (1) has a Mw ranging from about 10,000 g/mol to about 200,000 g/mol and has a polydispersity of 1.00 to about 1.20.