Towards chiral polystyrene based materials: controlled polymerization of p-(2,2′-diphenylethyl)styrene

Hohberger, Christiane; Beckerle, Klaus; Okuda, Jun

doi:10.1039/b9py00286c

Cited by 7 publications

(3 citation statements)

References 58 publications

(2 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since the possibility to synthesize iso- and syndiotactic polystyrenes was fully appreciated in the 1950s and 1980s, respectively, owing to the pioneering works of Ziegler–Natta and Ishihara, , the investigations into the polymerization of styrene (St) in a more active and stereospecific manner have led to the discovery of various homogeneous metallocene, half-metallocene, and non-metallocene group 3 and 4 transition metal based catalysts. − In spite of these marvelous achievements, stereospecific polymerizations of styrene derivatives bearing polar groups have been far from successful. The efficient catalysts for St polymerization are based mainly on hard Lewis-acidic transition metals that are swiftly killed by the Lewis-basic polar groups.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Stereospecific Polymerization of a Novel Bulky Styrene Derivative

Wang

Liu

et al. 2016

Macromolecules

View full text Add to dashboard Cite

A novel vinylbiphenyl monomer, 2-methoxy-5-phenylstyrene (MOPS), was designed and efficiently synthesized to investigate the stereospecific polymerization of bulky and polar styrenic derivative. Regardless of its large side group and electron-donating o-methoxy substituent, this compound showed a high polymerizability and was readily converted to the corresponding polymers with moderate to high molecular mass through radical, anionic, and coordination polymerizations. The resultant polymers were characterized by a combination of 1H/13C NMR spectrometry, thermal analysis, and wide-angle X-ray diffraction. Radical polymerization initiated by AIBN in toluene at 60 °C produced a syndiotactic-rich (rr = 0.37) polymer as most bulky vinyl monomers, whereas anionic polymerizations induced by n-BuLi yielded only isotactic-rich polymers no matter if polar tetrahydrofuran (−78 °C, mm = 0.54) or apolar toluene (−40 °C, mm = 0.78) was employed as the solvent. The isotactic-rich microstructure obtained by anionic polymerization in polar solvent at low temperature, the condition that usually leads to syndiotactic-rich polymer, manifested the strong interactions between the o-methoxy groups of the growing chain end and the penultimate unit with the lithium counterion. Highly isotactic (mm = 0.95) and perfect syndiotactic (rr > 0.99) polymers were obtained via coordination polymerizations in toluene at ambient temperature with the β-diketiminatoyttrium precursor (I) and the heterocyclic-fused cyclopentadienylscandium complex (III) as the catalytic precursor, respectively. All the polymers were thermally stable with 5% weight loss temperatures above 360 °C. They underwent glass transitions in the temperature range of 124–140 °C depending on the tacticity, much higher than polystyrene, implying the dominant role of congestion effect of large side groups on the segment movement restriction of polymer chain. Both isotactic and syndiotactic polymers were crystalline and had melting points higher than 300 °C, although the atactic and less stereoregular polymers were amorphous. The facile synthesis in conjunction with stereostructure tailorability, high thermal stability, glass transition temperature, and melting point makes the polymer a promising candidate for not only helical functional material but also engineering plastics.

show abstract

Section: Introductionmentioning

confidence: 99%

Synthesis and Stereospecific Polymerization of a Novel Bulky Styrene Derivative

Wang

Liu

et al. 2016

Macromolecules

View full text Add to dashboard Cite

show abstract

“…To obtain PDPES with a well-defined polymer chain structure, Okuda et al [ 22 ] synthesized it through radical and coordination Polymerizations. However, these polymerization processes were not well-controlled (PDPES yield = 7–62 wt%; polydispersity index [PDI] = 1.37–2.21), and little information has been reported concerning the anionic polymerization of DPES.…”

Section: Introductionmentioning

confidence: 99%

Anionic polymerization of p-(2,2′-diphenylethyl)styrene and applications to graft copolymers

Huang

Han

et al. 2016

Designed Monomers and Polymers

View full text Add to dashboard Cite

Well-controlled anionic polymerization of an initiator-functionalized monomer, p-(2,2′-diphenylethyl)styrene (DPES), was achieved for the first time. The polymerization was performed in a mixed solvent of cyclohexane and tetrahydrofuran (THF) at 40 °C with n-BuLi as initiator. When the volume ratio of cyclohexane to THF was 20, the anionic polymerization of DPES showed living polymerization characteristics, and well-defined block copolymer PDPES-b-PS was successfully synthesized. Furthermore, radical polymerization of methyl methacrylate in the presence of PDPES effectively afforded a graft copolymer composed of a polystyrene backbone and poly(methyl methacrylate) branches. The designation of analogous monomers and polymers was of great significance to synthesize a variety of sophisticated copolymer and functionalize polymer materials.

show abstract

“…Among them, polystyrenes have several advantages such as good transparency, low cost, and amenability to vary the functionalization and processing. These features make polystyrenes24–41 one of the most important candidates for optical applications.…”

Section: Introductionmentioning

confidence: 99%

Facile synthesis of high refractive index thiophene‐containing polystyrenes

Konishi

2011

J of Applied Polymer Sci

View full text Add to dashboard Cite

High refractive index polymer films have been extensively investigated because of their wide application potentials. We now designed thiophene-containing polystyrene as colorless and transparent high-refractiveindex thin film. The copolystyrenes were synthesized by general radical polymerization with controlled mole ratios 0 : 10, 1 : 9, 3 : 7, 5 : 5, 7 : 3, 9 : 1, 10 : 0 (styrene : p-bromostyrene), respectively. Next, the thiophene-containing polystyrenes were synthesized by Suzuki-Miyaura coupling reaction. The chemical structures of synthesized thiophene-containing polystyrene in accordance with ratios were confirmed by using 1 H-NMR, 13C-NMR, and FTIR. The effect of the thiophene units on refractive index according to copolymer ratios were confirmed by using prism coupler. The thiophene-containing polystyrene showed improved refractive index ranging from 1.58 to 1.67 and birefringence in the range of 0.0001-0.0019. The thermal stability and thermal behaviors of thiophene-containing polystyrene also can be confirmed by TGA and DSC. The polymers have high glass transition temperature in the range of 108 C-177 C.

show abstract

Towards chiral polystyrene based materials: controlled polymerization of p-(2,2′-diphenylethyl)styrene

Cited by 7 publications

References 58 publications

Synthesis and Stereospecific Polymerization of a Novel Bulky Styrene Derivative

Synthesis and Stereospecific Polymerization of a Novel Bulky Styrene Derivative

Anionic polymerization of p-(2,2′-diphenylethyl)styrene and applications to graft copolymers

Facile synthesis of high refractive index thiophene‐containing polystyrenes

Contact Info

Product

Resources

About