Robust Cross-Linked Stereocomplexes and C<sub>60</sub> Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.‐X.

doi:10.1021/jacs.6b04064

Cited by 32 publications

(48 citation statements)

References 103 publications

(51 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…190 A more impressive example involved the inclusion of C 60 fullerene within a cross-linked methacrylate complex. 343 Interestingly, the inclusion complex exhibited a novel transition (T m inclusion complex = 205 °C) that was not present in the fullerene, homopolymer, or the annealed blend.…”

Section: Pmmamentioning

confidence: 98%

Stereochemical enhancement of polymer properties

et al. 2019

View full text Add to dashboard Cite

The importance of stereochemistry to the function of molecules is generally well understood. However, to date, control over stereochemistry and its potential to influence properties of the resulting polymers are, as yet, not fully realised. This review focuses on the state-of-the-art with respect to how stereochemistry in polymers has been used to influence and control their physical and mechanical properties as well as begin to control their function. A brief overview of the synthetic methodology by which to access these materials is included, with the main focus directed towards stereochemical control over properties such as mechanical, biodegradation and conductivity. Additionally, the advances being made towards enantioseparation, enantioselective catalyst supports and stereo-directed transitions are discussed. Finally, we also consider the opportunities that the rich stereochemistry of sustainably-sourced monomers could offer in this field. Where possible, parallels and general design principles are drawn together to identify opportunities and limitations that these approaches may present in their effects on materials properties, performance and function.

show abstract

Section: Pmmamentioning

confidence: 98%

Stereochemical enhancement of polymer properties

et al. 2019

View full text Add to dashboard Cite

show abstract

“…For instance, Desroches et al previously reported the successful quantitative thiol‐ene coupling of mercaptoethanol on OLA unsaturations (Desroches et al, ). Alternatively to the modification of monomers, this reaction can also be employed in a postpolymerization functionalization approach, if the polymer still contains vinyl groups after polymerization (Hoyle and Bowman, ; Vidal et al, ; Vidal et al, ). Then, thiol‐ene coupling of OLA with alkyl thiols containing long aliphatic chains could yield suitable highly hydrophobic monomers for providing high performant polymer‐based VII for MPO.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Alkyl Sulfur‐Functionalized Oleic Acid‐Based Polymethacrylates and Their Application as Viscosity Index Improvers in a Mineral Paraffinic Lube Oil

Lomège

Négrell

Robin

et al. 2019

J Americ Oil Chem Soc

View full text Add to dashboard Cite

This work describes the synthesis of alkyl sulfur‐functionalized polymethacrylate‐based Viscosity Index Improvers (VII) derived from oleic acid (OLA) for mineral paraffinic lubricating oils. In this strategy, OLA was first quantitatively ramified by alkyl thiols containing long aliphatic chains through thiol‐ene coupling as demonstrated by 1H NMR spectroscopy with the complete consumption of OLA internal double bonds. The resulting alkyl sulfur‐functionalized OLA‐based derivatives were methacrylated through Steglich esterification in order to afford highly suitable hydrophobic OLA‐based monomers which, as far as we know, have not been described yet in the current literature. High polymethacrylate molecular weights were reached through radical polymerization despite the long alkyl pendant chains contained in their backbones. Finally, the resulting alkyl sulfur‐functionalized OLA‐based polymethacrylates have been blended in a mineral paraffinic oil (MPO) of reference at 5 wt% and evaluated as VII. Rheological measurements revealed that polymer thickening powers were significantly improved in oil with temperature and promoted by increasing the pendant alkyl thiol contained in polymer backbones. Moreover, the viscosity index of MPO was significantly improved with the addition of both synthesized homopolymers which confirmed their efficiency as VII. In the meantime, these results have been compared with a previously reported polymer, the poly(2‐[methacryloyloxy]ethyl oleate) (PMAEO), which demonstrated a lower VII efficiency compared with its analogous polymethacrylates containing an additional alkyl chain in their pendant chains.

show abstract

“…Limited catalyst systems have been developed for the chemoselective polymerization of polar divinyl monomers under mild conditions [ 15 ]. Chen’s group recently reported an elegant example of the chemoselective polymerization of polar divinyl monomers by using chiral ansa-zirconocene enolates, affording a highly stereotactic polymer [ 17 , 18 ]. The same group achieved complete chemoselectivity in the polymerization of multivinyl-functionalized γ -butyrolactones by utilizing N -heterocyclic carbene (NHC) catalysts [ 19 ].…”

Section: Introductionmentioning

confidence: 99%

Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs

Dong

et al. 2018

Molecules

View full text Add to dashboard Cite

This work reports the chemoselective polymerization of polar divinyl monomers, including allyl methacrylate (AMA), vinyl methacrylate (VMA), and 4-vinylbenzyl methacrylate (VBMA), by using simple Lewis pairs comprised of homoleptic rare-earth (RE) aryloxide complexes RE(OAr)3 (RE = Sc (1), Y (2), Sm (3), La (4), Ar = 2,6-tBu2C6H3) and phosphines PR3 (R = Ph, Cy, Et, Me). Catalytic activities of polymerizations relied heavily upon the cooperation of Lewis acid and Lewis base components. The produced polymers were soluble in common organic solvents and often had a narrow molecular weight distribution. A highly syndiotactic poly(allyl methacrylate) (PAMA) with rr ~88% could be obtained by the scandium complex 1/PEt3 pair at −30 °C. In the case of poly(4-vinylbenzyl methacrylate) (PVBMA), it could be post-functionalized with PhCH2SH. Mechanistic study, including the isolation of the zwitterionic active species and the end-group analysis, revealed that the frustrated Lewis pair (FLP)-type addition was the initiating step in the polymerization.

show abstract

Robust Cross-Linked Stereocomplexes and C₆₀ Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

Cited by 32 publications

References 103 publications

Stereochemical enhancement of polymer properties

Stereochemical enhancement of polymer properties

Synthesis of Alkyl Sulfur‐Functionalized Oleic Acid‐Based Polymethacrylates and Their Application as Viscosity Index Improvers in a Mineral Paraffinic Lube Oil

Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs

Contact Info

Product

Resources

About

Robust Cross-Linked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

Cited by 32 publications

References 103 publications

Stereochemical enhancement of polymer properties

Stereochemical enhancement of polymer properties

Synthesis of Alkyl Sulfur‐Functionalized Oleic Acid‐Based Polymethacrylates and Their Application as Viscosity Index Improvers in a Mineral Paraffinic Lube Oil

Chemoselective Polymerization of Polar Divinyl Monomers with Rare-Earth/Phosphine Lewis Pairs

Contact Info

Product

Resources

About

Robust Cross-Linked Stereocomplexes and C₆₀ Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization