Tapered Multiblock Star Copolymers: Synthesis, Selective Hydrogenation, and Properties

Two series of well-defined multiblock four-arm tapered star copolymers with “arms” of the type poly(styrene)-block-poly(isoprene-grad-styrene), (SI/S)₄, were synthesized on a multigram scale with short reaction times. Targeted molecular weight (M) values ranged from 80 to 240 kg mol–¹ with polystyrene (PS) compositions of 40 and 60 wt %. Narrowly distributed (Đ = 1.04–1.12) copolymers were obtained regardless of M and without additional purification beyond precipitation. At sufficiently high M, members of the 40 wt % PS series possessed either a cylindrical or bicontinuous morphology, whereas the 60 wt % PS series yielded lamellae. The star copolymers outperformed their corresponding linear…

Rapid one-pot synthesis of tapered star copolymers via ultra-fast coupling of polystyryllithium chain ends

Highly efficient stoichiometric coupling of sterically hindered polystyryllithium (PS-Li) chain ends was achieved using tetra[3-(chloro-dimethylsilyl)propyl]silane (TCDMSPS) as the linking agent. Based on the disparate reactivities of isoprene (I, rI = 11.0) and styrene (S, rS = 0.049) in the anionic copolymerization in nonpolar media, poly(isoprene0.5-grad-styrene0.5) (P(I0.5-grad-S0.5)) tapered 4-arm star copolymers were synthesized in only two steps. The tapered 4-arm star copolymers (Mtargetedw = 40 to 160 kg mol−1) were synthesized with high star functionalities f (Mw,star/Mw,arm = 3.68–3.98), low dispersity (Đ = 1.06–1.15) and minimal residual precursor content (2–8 wt%), avoiding fra…

Copolymerization of Isoprene with p-Alkylstyrene Monomers: Disparate Reactivity Ratios and the Shape of the Gradient

The statistical copolymerization of isoprene with p-ethyl- (p-ES), p-isopropyl- (p-iPS), and p-tert-butylstyrene (p-tBS) initiated by sec-butyllithium in cyclohexane was investigated with respect to kinetics, reactivity ratios, and formation of tapered block copolymers with pronounced monomer gradient. An efficient synthetic route to the monomers was developed on a multigram scale, relying on the precipitation of the side-product triphenylphosphine oxide at low temperature. The copolymerization kinetics and resulting molecular weight distributions were analyzed. The dispersity, Đ, of the copolymers depends on the p-alkyl substituent, the the degree of polymerization Pn and the comonomer mol…

Functional Group Distribution and Gradient Structure Resulting from the Living Anionic Copolymerization of Styrene and para-But-3-enyl Styrene

The functional group distribution along the polymer backbone resulting from the living anionic copolymerization of styrene (S) and para-but-3-enyl styrene (pBuS) was investigated in cyclohexane at room temperature. A variety of copolymers with different comonomer contents x(S) = 0–0.84 have been synthesized with molecular weight dispersities Mw/Mn ≤1.12. All polymers have been characterized in detail by 1H NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC). A detailed understanding of the monomer sequence distribution during the copolymerization was achieved by real-time 1H NMR spectroscopy. This technique permits us to determine the changing …

Synthesis and Solution Processing of Nylon‐5 Ferroelectric Thin Films: The Renaissance of Odd‐Nylons?

A Nonconventional Approach toward Multihydroxy Functional Polystyrenes Relying on a Simple Grignard Reagent

Capitalizing on the inertness of styrene toward Grignard reagents, 4-vinylphenylmagnesium bromide was utilized for the rapid and convenient preparation of the protected monomer 2,2-dimethyl-4-(4-vi...

Solution-processed transparent ferroelectric nylon thin films

We have developed a method to solution process strongly hydrogen-bonded odd nylons into ferroelectric thin films.

Tapered Multiblock Copolymers Based on Farnesene and Styrene: Impact of Biobased Polydiene Architectures on Material Properties

The reactivity of the biobased monomer β-farnesene in the statistical anionic copolymerization with styrene and the effect of the bottlebrush-like polyfarnesene structure on the phase separation be...