Self-Assembly of Low-Molecular-Weight Asymmetric Linear Triblock Terpolymers: How Low Can We Go?

Abstract

The synthesis of two (2) novel triblock terpolymers of the ABC type and one (1) of the BAC type, where A, B and C are chemically different segments, such as polystyrene (PS), poly(butadiene) (PB1,4) and poly(dimethylsiloxane) (PDMS), is reported; moreover, their corresponding molecular and bulk characterizations were performed. Very low dimensions are evident from the characterization in bulk from transmission electron microscopy studies, verified by small-angle X-ray data, since sub-16 nm domains are evident in all three cases. The self-assembly results justify the assumptions that the high Flory–Huggins parameter, χ, even in low molecular weights, leads to significantly well-ordered structures, despite the complexity of the systems studied. Furthermore, it is the first time that a structure/properties relationship was studied for such systems in bulk, potentially leading to prominent applications in nanotechnology and nanopatterning, for as low as sub-10 nm thin-film manipulations.

Thermal and Bulk Properties of Triblock Terpolymers and Modified Derivatives towards Novel Polymer Brushes

“…The purification procedures of the involved reagents, including solvents [benzene (99%), tetrahydrofuran (99%)], monomers [styrene (99%), hexamethylcyclotrisiloxane (D 3 ) (98%), 1,3-butadiene (99%)], termination agent [methanol (98%)], 1,2-dipiperidinoethane [dipip (98%)], and initiator [ secondary -BuLi ( sec -Buli, 1.4 M in cyclohexane)] are documented elsewhere [ 29 , 41 ]. 9-borabicyclo[3.3.1]nonane or 9-BBN (0.5 M in tetrahydrofuran), hydrogen peroxide (H 2 O 2 ) and sodium hydroxide (NaOH) were used as received.…”

“…The instrumentations with which molecular characterization experiments were performed, including SEC, VPO, 1 H-NMR, and FT-IR, have already reported in our previous works [ 30 , 41 ].…”

“…To overcome this limitation, several strategies have been employed, such as the use of homopolymer brushes (hydroxyl-terminated PS and/or PDMS), pre-patterned surfaces, solvent annealing, etc. [ 1 , 37 , 38 , 39 , 40 , 41 ].…”

“…Taking into consideration the previous study conducted by Avgeropoulos’ group [ 41 ] where, among others, the bulk properties of PS- b -PB 1,4 - b -PDMS or PB 1,4 - b -PS- b -PDMS were reported, it is straightforward that low molecular weight triblock terpolymers are not frequently encountered in the relative literature and the importance of high χ/low N (N: degree of polymerization) terpolymers in microelectronics could be proven most vital.…”

Bicontinuous Gyroid Phase of a Water-Swollen Wedge-Shaped Amphiphile: Studies with In-Situ Grazing-Incidence X-ray Scattering and Atomic Force Microscopy

“…10 and 100 nm for BCP-based systems [ 24 ], while it can rarely exceed several nanometers for LC systems [ 25 ]. In some instances, it is interesting to make the characteristic distances of both systems closer to each other, i.e., by increasing the sizes of the LC systems and/or by bringing down the dimensions of phases generated by the BCPs in order to make them interesting for the developing areas of nanotechnologies and nanopatterning [ 26 ].…”