Microphase Separation of Polybutyrolactone-Based Block Copolymers with Sub-20 nm Domains

Abstract

Polybutyrolactone tri-and di-block copolymers with well-defined structures and narrow molar distributions were prepared by trifluoromethane sulfonic acid-organocatalyzed ringopening polymerization of β-butyrolactone initiated with dihydroxylated poly(hydrogenated)butadiene and hydroxylated polystyrene. Study of the phase separation behavior of these block copolymers in the bulk and in thin film shows their ability to segregate even for low molecular weights, giving rise to spherical, cylindrical and lamellar morphologies with periodicities in the range of 10-20 nm. Estimation of the Flory-Huggins interaction parameter form the order-to-disorder transition temperatures reveals values in the same range or higher than other block copolymers associating biodegradable and polyolefin blocks

Polystyrene Chain Growth Initiated from Dialkylzinc for Synthesis of Polyolefin-Polystyrene Block Copolymers

“…The ethylene/propylene mixed gas was purified over trioctylaluminum (0.6 M in methylcyclohexane) in a bomb reactor (2.0 L). 1 H NMR (600 MHz) and 13 C NMR (150 MHz) spectra were recorded on a JEOL ECZ600 instrument. The gel permeation chromatography (GPC) data were Scheme 1.…”

“…The ethylene/propylene mixed gas was purified over trioctylaluminum (0.6 M in methylcyclohexane) in a bomb reactor (2.0 L). 1 H NMR (600 MHz) and 13 C NMR (150 MHz) spectra were recorded on a JEOL ECZ600 instrument. The gel permeation chromatography (GPC) data were obtained in 1,2,4-trichlorobenzene at 160 • C using a PL-GPC 220 system equipped with an RI detector and two columns [PLgel mixed-B 7.5 × 300 mm from Varian (Polymer Lab)].…”

“…The following are available online at http://www.mdpi.com/2073-4360/12/3/537/s1, Figure S1: 13 C spectrum of 1-octyllithium prepared from (1-octyl) 2 Zn in C 6 D 6 , Figure S2: 1 H and 13 C NMR spectra of 2-ethylhexyllithium prepared from (2-ethylhexyl) 2 Zn in C 6 D 6 , Figure S3: GPC curve after styrene polymerization performed with no addition of PMDTA (Entry 1 in Table 1), Figure S4: GPC curves before and after styrene polymerization, Figure S5: 1 H NMR spectrum (C 6 D 6 ) of the lithium species generated in the pot of "1-octene + n-BuLi + PMDTA" in methylcyclohexane, Figure S6: 1 H NMR spectrum (C 6 D 6 ) of the species generated by quenching the reaction pot of "1-octene + n-BuLi + PMDTA" in methylcyclohexane with H 2 O or D 2 O, Figure S6: 1 H NMR spectrum (C 6 D 6 ) of the species generated by quenching the reaction pot of "1-octene + n-BuLi + PMDTA" in methylcyclohexane with H 2 O or D 2 O, Figure S8: 1 H spectrum of "sec-BuLi + PMDTA" in C 6 D 12 (30 min), Figure S9: 1 H spectrum of C6D5Li × (PMDTA) prepared in the reaction pot of "n-BuLi + PMDTA" in C 6 D 6 , Figure S10: 1 H spectrum (C 6 D 6 ) of the lithium species in the pot of "n-BuLi + PMDTA" in 1-octene, Figure S11: GPC curves before and after styrene polymerization, Figure S12: DSC thermogram of PO-block-PS (Entry 5 in Table 3).…”

“…However, PO-based block copolymers have rarely been synthesized because α-olefins cannot be polymerized by either anionic or radical initiators [4][5][6]. The lack of versatile synthetic tools has promoted the development of multistep routes for the syntheses of PO-based block copolymers [7][8][9][10][11][12][13][14][15]. For example, polystyrene-block-poly(ethylene-co-1-butene)-block-polystyrene is produced industrially via a two-step method for the industrial production of OBCs is based on coordinative chain transfer polymerization (CCTP).…”

Microphase separation/crosslinking competition-based ternary microstructure evolution of poly(ether-b-amide)

“…Due to the thermodynamic immiscibility between the segments, several long-range order structures can be formed within a sub-micrometer scale (known as microphase separation). [1][2][3][4][5] With extensive research, the morphology of different phases is greatly affected by the Flory interaction parameters between the two segments, composition, and the overall degree of polymerization. [6][7][8][9][10][11][12][13][14] Furthermore, the material properties such as modulus, [15][16][17] conductivity, 18,19 and rheological properties 20,21 can be enhanced at the order states.…”