Synthesis of a Multiblock Copolymer of cis‐1,4‐Polybutadiene and Poly(3‐buten‐1‐ol)

Abstract

Synthesis of a multiblock copolymer composed of cis‐1,4‐polybutadiene (PBd) segments and poly(3‐buten‐1‐ol) segments is performed via successive hydroboration and oxidation of cis‐1,4/syn‐1,2‐multiblock PBd. The ratio of functionalization can be controlled by changing the amount of the borane reagent. The obtained polymer shows two distinctive glass‐transition temperatures, which correspond to the cis‐1,4‐PBd block and the poly(3‐buten‐1‐ol) block. These thermal properties clearly show that the functionalization of the PBd proceeds keeping the elastic property derived from cis‐1,4 segment.

Hydrogen bonding and thermoplastic elastomers – a nice couple with temperature-adjustable mechanical properties

“…4,[15][16][17][18][19][20] Not only the functionalization of the precursor building blocks (telechelic units) for the polymer chains and networks is today synthetically quite feasible, 21,22 but also the post modification of a polymer along the chain. This offers the possibility to tune the properties of the polymer [23][24][25][26][27] and thus widens the range of potential applications eminently. 26,[28][29][30][31] For instance, the combination of thermoplastic polystyrene and elastomeric polybutadiene provides thermoplastic elastomers (TPEs) with the advantage of a good and adjustable balance between elasticity and rigidity in the resulting material.…”

Orthogonal functionalization of alternating polyesters: selective patterning of (AB)n sequences

“…Our attention was drawn to alkene hydroboration-oxidation as an efficient means to install hydroxyl substituents because it has been shown to be compatible with ester linkages, as demonstrated by its successful application to functionalize polyhydroxyalkanoates. [51][52][53][54][55] In the 1980s Brown and co-workers established that primary and secondary alkenes showed up to three orders of magnitude difference in rates of hydroboration when using sterically hindered boranes. 56,57 We reasoned that a polyester containing both primary and secondary alkene groups might undergo selective reaction at the primary alkene sites (Scheme 1).…”

Organoborane Strategy for Polymers Bearing Lactone, Ester, and Alcohol Functionality

“…Nishikawa and Ouchi recently described a similar approach to poly­(α-methyl vinyl alcohol) via isopropenyl pinacol boronate polymerization . Postpolymerization borylation, either by hydroboration of alkenyl residues − or CH activation, − is a well-explored strategy for polyolefin functionalization.…”