Investigation of 1,1‐diphenylethylene Oligomerization in the End‐Capping Reaction of Poly(styryl)lithium

Abstract

Summary: The possible oligomerization of 1,1-diphenylethylene (DPE) in the endcapping reaction of poly(styryl)lithium (PSLi) was studied in hydrocarbon solvents using excess DPE ( 16 mol-eq); the effect of addition of THF (30 mol-eq Lewis base) and extended times of reaction (8-24 h) were also investigated. The characterization of the polymers was made by size exclusion chromatography (SEC), proton nuclear magnetic resonance spectroscopy (1H NMR) and matrix-assisted laser desorption/ ionization time of flight mass spectrometry (MALDI-TOF MS). MALDI-TOF mass spectrometric results revealed the absence of DPE oligomerization under the reaction conditions used in this study.

Investigation of the Locked‐Unlocked Mechanism in Living Anionic Polymerization Realized with 1‐(Tri‐isopropoxymethylsilylphenyl)‐1‐phenylethylene

“…The mechanism of chain propagation in nonpolar solvents and at room temperature has been thoroughly investigated over the past 60 years . The kinetic control can be used in block polymerization to effectively cap polymers with functional end groups, and this knowledge has guided both industrial manufacturing and scientific research. As a typical methodology explored in LAP, 1,1‐diphenylethylene (DPE) chemistry expands access to functionalized polymers because of the unique characteristics of DPE derivatives .…”

Synthesis of Bottlebrush Polystyrenes with Uniform, Alternating, and Gradient Distributions of Brushes Via Living Anionic Polymerization and Hydrosilylation

“…How to synthesize polymers with well-defi ned distribution of monomers sequence (which was defi ned as "sequence-controlled" polymers) [ 28 ] has become a novel area for polymer synthetic chemistry. [28][29][30][31][32][33][34] Taking into consideration the special copolymerization characteristic of DPE derivatives (they cannot be homopolymerized, but the dimerization could be observed under certain conditions, [ 35 ] investigations on the construction of functionalized telechelic polymers, exact combs, DendriMacs, etc., have been executed. [36][37][38][39] Meanwhile, well-defi ned control of monomer sequence with DPE derivatives as monomers has been carried out utilizing living anionic polymerization, the approximately alternating in-chain functionalized polymers with DPE functional derivatives as monomer have been synthesized successfully.…”