Highly <i>Cis</i>-1,4-Selective Living Polymerization of 3-Methylenehepta-1,6-diene and Its Subsequent Thiol–Ene Reaction: An Efficient Approach to Functionalized Diene-Based Elastomer

Li, Lei; Li, Shihui; Cui, Dongmei

doi:10.1021/acs.macromol.5b02654

Cited by 38 publications

(29 citation statements)

References 63 publications

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“…Postpolymerization modification was widely used to prepare functional elastomers. Functionalization of poly(3‐methylenehepta‐1,6‐diene) by reacting the pendant vinyl groups with various polar groups via a light‐mediated thiolene method allowed the synthesis of functional butadiene‐based materials with greater hydrophilicity . An epoxide‐functionalized poly(isobutylene‐ co ‐isoprene) derivative was also used to cleanly prepare a specific exo ‐diene, allowing subsequent functionalization by Diels–Alder cycloaddition and/or ring opening of maleic anhydride adducts.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of β‐myrcene/glycidyl methacrylate statistical and amphiphilic diblock copolymers by SG1 nitroxide‐mediated controlled radical polymerization

Métafiot

Gérard

Defoort

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Bulk nitroxide-mediated polymerization (NMP) of bmyrcene (My)/glycidyl methacrylate (GMA) mixtures with varying GMA molar feed fraction (f GMA,0 5 0.10-0.91) was accomplished at 120 8C, initiated by SG1-based alkoxyamine bearing a N-succinimidyl ester group (NHS-BlocBuilder). Low dispersity My/GMA copolymers ( -D < 1.56) with slight number-average molecular weights (M n s) deviations from predicted values (M n,theo with M n /M n,theo > 70%) were obtained. The copolymerization was revealed to be statistical, confirmed via Fineman-Ross (r My 5 0.80 6 0.31 and r GMA 5 0.71 6 0.15) and Kelen-T€ ud€ os (r My 5 0.48 6 0.12 and r GMA 5 0.53 6 0.18) approaches. Glass transition temperature (T g ) of the statistical P(My-stat-GMA)s increased from 277 to 143 8C as the GMA molar fraction incorporated (F GMA ) increased from 0.10 to 0.90. High SG1 chain-end fidelity for My-rich and GMA-rich P(My-stat-GMA)s was assessed by phosphorus nuclear magnetic resonance ( 31 P NMR, SG1 fraction >69 mol %) and chain-extensions in toluene with My, GMA and styrene (S) (monomodal shift in M n ). Last, diblock P(My-b-GMA) was made and treated with morpholine to produce amphiphilic copolymer able to self-organize into micelles.

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Section: Introductionmentioning

confidence: 99%

Synthesis of β‐myrcene/glycidyl methacrylate statistical and amphiphilic diblock copolymers by SG1 nitroxide‐mediated controlled radical polymerization

Métafiot

Gérard

Defoort

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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“…The thermal history difference in the polymers was eliminated by first heating the specimen to 70 °C, cooling at 10 °C min −1 to −110 °C, and then a second heating from −110 to 70 °C at 10 °C min −1 was performed. The lutetium complexes 1 – 3 and the MHD monomer were prepared according to literature.…”

Section: Methodsmentioning

confidence: 99%

Chemo‐ and stereoselective polymerization of 3‐methylenehepta‐1,6‐Diene and Its thiol‐ene modification

Cui

2017

J. Polym. Sci. Part A: Polym. Chem.

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Here we report on the coordination polymerization of a vinyl-functionalized butadiene monomer, 3-methylenehepta-1,6diene (MHD) with exclusive conjugated diene chemoselectivity, high 1,2-regioselectivity and moderate isotacticity (1,2selectivity > 99%, mm triad 5 93%). Random copolymers of MHD and other conjugated diene (isoprene or myrcene) are also synthesized. The pendent vinyl groups of MHD homo or copolymers could be quantitatively converted into various functional groups via thiol-ene click reaction. The resulting functionalized polybutadiene-based material display versatile thermal and surface properties.

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“…The trimethylsilylmethyl‐substituted scandium and yttrium complexes, Pyr ( Cy PNP)M(CH 2 SiMe 3 ) 2 (M = Sc, Y), have been used as pre‐catalysts for the hydrogenation of alkenes and alkynes, while related Cbz ( R PNP)‐coordinated group 3 and lanthanide alkyls were observed to effectively catalyze cis‐1,4‐selective living polymerization reactions of 1,3‐dienes …”

Section: Pnp Pincers and Their Reactivity Patternsmentioning

confidence: 99%

Phosphines and N‐Heterocycles Joining Forces: an Emerging Structural Motif in PNP‐Pincer Chemistry

2020

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Aminodiphosphines and their monoanionic amido derivatives are among the most widely used tridentate ligands. A good share of these ligands, in particular the ones that are based on a rigid N‐heterocyclic core, is predisposed to coordinate in a meridional fashion. Negatively charged derivatives of these meridionally coordinating N‐heterocyclic ligands satisfy all the criteria for PNP pincer scaffolds. Herein, these ligands and their coordination chemistry is reviewed from the perspective of coordination chemistry. For our discussion, ligands containing a protonated N‐heterocycle (e.g. pyrrole‐ or carbazole‐based PNP scaffolds) are to be distinguished from their counterparts that do not contain such an NH‐functionality (e.g. pyridine‐ or triazine‐based PNP scaffolds). Different synthetic methodologies for the preparation of PNP pincer complexes are presented and shown to often depend on the presence or absence of the aforementioned NH‐proton. The different reactivity patterns of the resulting complexes are sub‐divided into two categories, namely into metal‐centered reactions and reactions that result in a chemical transformation at the metal and the ligand. The latter represent ligand‐cooperative transformations, which often play a key role in catalysis, and are showcased by discussing selected applications in catalysis. It will become evident in this review that this relatively young research field is still emerging and far from reaching maturity. Finally, a brief overview on ligand/metal combinations that have not been explored to date is provided, to stimulate future research on PNP pincers featuring a central N‐heterocycle.

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Highly Cis-1,4-Selective Living Polymerization of 3-Methylenehepta-1,6-diene and Its Subsequent Thiol–Ene Reaction: An Efficient Approach to Functionalized Diene-Based Elastomer

Cited by 38 publications

References 63 publications

Synthesis of β‐myrcene/glycidyl methacrylate statistical and amphiphilic diblock copolymers by SG1 nitroxide‐mediated controlled radical polymerization

Synthesis of β‐myrcene/glycidyl methacrylate statistical and amphiphilic diblock copolymers by SG1 nitroxide‐mediated controlled radical polymerization

Chemo‐ and stereoselective polymerization of 3‐methylenehepta‐1,6‐Diene and Its thiol‐ene modification

Phosphines and N‐Heterocycles Joining Forces: an Emerging Structural Motif in PNP‐Pincer Chemistry

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