No abstract

The metal-free polymerization of propylene oxide (PO) using a special class of alkene—N-heterocyclic olefins (NHOs)—as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal-free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity (ĐM<1.09). NHOs with an unsaturated backbone are essential for polymerization to occur, while substitution at the exocyclic carbon atom has an impact on the reaction pathway and ensures the suppression of side reactions.

In this work, the activity of N-heterocyclic olefins (NHOs), a newly emerging class of organopolymerization catalyst, is investigated to affect the metal-free polymerization of lactones and trimethylene carbonate (TMC). A decisive structure–activity relationship is revealed. While catalysts of the simplest type bearing an exocyclic CH2 moiety polymerize l-lactide (l-LA) and δ-valerolactone (δ-VL) in a non-living and non-quantitative manner, the introduction of methyl substituents on the exocyclic carbon radically changes this behavior. 2-Isopropylidene-1,3,4,5-tetramethylimidazoline is found to be highly active for a range of monomers such as l-LA, δ-VL, ε-caprolactone (ε-CL), and TMC, with quantitative conversion occurring within seconds with catalyst loadings of just 0.2 mol %. The high activity of this NHO further enables the ring-opening polymerization (ROP) of the macrolactone ω-pentadecalactone (PDL). However, this broad applicability is offset by a lack of control over the polymerizations, including side reactions as a consequence of its strong basicity. To overcome this, a saturated, imidazolinium-derived analogue was synthesized and subsequently demonstrated to possess a harnessed reactivity which enables it to polymerize both l-LA and TMC in a controlled manner ( Đ M < 1.2). NMR spectroscopic and MALDI-ToF MS experiments highlight the differences in polymerization pathways for 2-methylene-1,3,4,5-tetramethylimidazoline, in which the exocyclic carbon is not substituted, in contrast to 2-isopropylidene-1,3,4,5-tetramethylimidazoline, with the former operating via its nucleophilicity and the latter acting as a base with enolizable δ-VL.

We extend the study of lowest moments, x and x 2 , of the parton distribution function of the nucleon to include those of the sea quarks; this entails a disconnected insertion calculation in lattice QCD. This is carried out on a 16 3 × 24 quenched lattice with Wilson fermion. The quark loops are calculated with Z 2 noise vectors and unbiased subtractions, and multiple nucleon sources are employed to reduce the statistical errors. We obtain 5σ signals for x for the u, d, and s quarks, but x 2 is consistent with zero within errors.We provide results for both the connected and disconnected insertions. The perturbatively renormalizedx for the strange quark at µ = 2 GeV is x s+s = 0.027 ± 0.006 which is consistent with the experimental result. The ratio of x for s vs. u/d in the disconnected insertion with quark loops is calculated to be 0.88 ± 0.07. This is about twice as large as the phenomenologically fitted x s+s x ū + x d from experiments whereū andd include both the connected and disconnected insertion parts. We discuss the source and implication of this difference.