Anionic Polymerization of Acrylic Monomers. 14. Carbon-13 and Lithium-7 NMR Characterization of the Complexation of Methyl .alpha.-Lithioisobutyrate with Various Lithium Cation-Binding Ligands in Tetrahydrofuran

Wang, Jinshan; Jérôme, Robert; Warin, R.; Zhang, H.; Teyssié, Philippe

doi:10.1021/ma00090a036

Cited by 38 publications

(59 citation statements)

References 3 publications

(5 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, their interaction with unimeric models has been studied in order to understand better how they modify the main characteristics of the lithium ester enolates (Scheme 13). The effect of these ligands on the charge distribution around the carbanion of MiBLi in THF has been approached by 13 C NMR spectroscopy [51]. Although the O-Li bond in lithium ester enolates is rather weak and highly polarized, the σ-type ligand known for lithium cation-binding and considered in this study (Scheme 13) do not show any significant σ coordination in THF, except for K211.…”

Section: Scheme 13 Polyether and Polyamine Ligands Used In Lapmentioning

confidence: 93%

See 1 more Smart Citation

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Zune

Jérôme

1999

Progress in Polymer Science

View full text Add to dashboard Cite

Ligation of the anionic species responsible for the polymerization (LAP) of alkyl(meth)acrylates has much contributed to improve polymerization control. This ligated anionic polymerization has been firstly studied by using model compounds, such as low molecular weight lithium ester enolates. Recently, effort has been devoted to the direct analysis of the species that propagate the anionic polymerization of (meth)acrylates. In addition to IR, multinuclear NMR spectroscopy has been very instrumental in the elucidation of the structure and aggregation of the active species and how these characteristic features are modified by the addition of various types of ligands. This substantial progress in the characterization of the polyalkyl(meth)acrylate anions, ligated or not, is reported in this review.

show abstract

Section: Scheme 13 Polyether and Polyamine Ligands Used In Lapmentioning

confidence: 93%

“…2. σ-type ligands, that form coordinative complexes with the metal counterion of the active species: crown ethers [50] and kryptands [51]. 3.…”

Section: Incentives To the Ligated Anionic Polymerization Of Polar Momentioning

confidence: 99%

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Zune

Jérôme

1999

Progress in Polymer Science

View full text Add to dashboard Cite

show abstract

“…1,1-Diphenylhexyllithium (DPHLi) was prepared by the reaction of a known amount of BuLi with a slight excess of diphenylethylene (DPE) in hexane at room temperature. DPHLi separated as a red precipitate and was washed twice with dry hexane and dried under vacuum for 4 h. It was characterized using NMR spectroscopy in THF-d 8 Similarly, tetrakis[tris(dimethylamino)phosphoranylidenamino]phosphonium enolate (EIBP 5 ) was synthesized by reacting the lithium enolate with little excess P 5 + Cl -in THF at -20 8C and the excess salt was filtered off. 13 C NMR, see Tab.…”

Section: Initiatorsmentioning

confidence: 99%

“…One possibility is the use of various ligands in conjunction with classical anionic initiators. r-Ligands, such as crown ethers 6) , cryptands 7,8) , tertiary amines 9,10) ; l-ligands, such as alkali alkoxides 11,12) halides 2, 13) , perchlorates 14,15) , aluminum alkyls [16][17][18][19] , and r, l-ligands, such as alkoxyalkoxides [20][21][22][23] , aminoalkoxides 24) , and silanolates [25][26][27] have been used with much success.…”

Section: Introductionmentioning

confidence: 99%

Anionic polymerization of methyl methacrylate using tetrakis[tris(dimethylamino)phosphoranylidenamino] phosphonium (P5+) as counterion in tetrahydrofuran

Baskaran

Müller²

2000

Macromol. Rapid Commun.

View full text Add to dashboard Cite

“…Crown ethers, amine cryptands, and pyridine all promote the formation of narrow-PDI poly(meth)acrylates by eliminating chain-end aggregation and promoting the formation of monomeric, highly reactive species (2,(62)(63)(64)(65)(66)(67). Large "metal free" organic counterions, including tetraalkylammoniums (68-70), tetraphenylphosphonium, and T4V (71) have also been employed to control polymerization at J p 4 + LiOEEM higher temperatures (0-20 °C) with reasonable success.…”

Section: Strategies For Living Polymerizationmentioning

confidence: 99%

The Organometallic Polymerization of (Meth)acrylates: An Overview

Boffa

2000

ACS Symposium Series

View full text Add to dashboard Cite

Metal-mediated (meth)acrylate polymerizations provide a good example of the versatility and importance of transition metal catalysis in polymer design. This chapter surveys several of these processes with respect to "living" behavior, experimental condition and monomer restrictions, and types of polymer architectures available.In addition to anionic methods, Group Transfer Polymerization (GTP) with silyl enolates or zirconocenes, organolanthanide-and aluminum porphyrin-initiated polymer ization, and Atom Transfer Radical Polymerization (ATRP) are discussed.Polymethacrylate and polyacrylate materials play an important role in our society. Almost two billion pounds of polymer products based on acrylic esters are produced each year for applications such as window plastics, dental materials, paints, contact lenses, fibers, and viscosity modifiers.Polymethacrylates-particularly poly(methyl methacrylate) (PMMA)-possess high strength, high impact resistance, excellent heat and chemical stability, and a highly amorphous nature which results in excellent optical clarity. For these reasons, they are used widely as building plastics (Plexiglas, Lucite). Polyacrylates are less rigid due to their lower glass transition temperatures, and as latex emulsions form the basis for durable automobile and house paints and coatings. Random copolymers of (meth)acrylates with vinylidene chloride (Sarari), acrylonitrile, and ethylene find applications as clothing fibers, tubing, gaskets, disposable gloves, and heat-and oil-resistant automotive elastomers.Despite the commercial utility of polymethacrylates and polyacrylates, refinements in synthetic methodology these macromolecules have lagged behind that of other polymers. The great majority of acrylic ester products in use today are still produced by radical polymerization, which allows little if any control over the fine points of the polymerization process. This is the result of the traditionally illcontrolled nature of acrylate polymerization. While chain termination and transfer side reactions may be largely eliminated for other monomers, such as styrene and dienes, through the use of controlled anionic polymerization, the (meth)acrylate ester

show abstract

Anionic Polymerization of Acrylic Monomers. 14. Carbon-13 and Lithium-7 NMR Characterization of the Complexation of Methyl .alpha.-Lithioisobutyrate with Various Lithium Cation-Binding Ligands in Tetrahydrofuran

Cited by 38 publications

References 3 publications

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Anionic polymerization of methyl methacrylate using tetrakis[tris(dimethylamino)phosphoranylidenamino] phosphonium (P5+) as counterion in tetrahydrofuran

The Organometallic Polymerization of (Meth)acrylates: An Overview

Contact Info

Product

Resources

About