Anionic polymerization

Bywater, S.

doi:10.1016/0079-6700(75)90003-9

Cited by 59 publications

(9 citation statements)

References 239 publications

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“…Die erstgenannten Reaktionen, Wie aus den Charakteristiken von Oligobutadienyl-und Oligoisoprenyllithium folgt, andert sich die Elektronendichteverteilung der Endglieder in polaren Medien zugunsten des C,-Atoms [42], was rnit den strukturellen Effekten der alternativen Richtungen (Gleichung (13) Die erstgenannten Reaktionen, Wie aus den Charakteristiken von Oligobutadienyl-und Oligoisoprenyllithium folgt, andert sich die Elektronendichteverteilung der Endglieder in polaren Medien zugunsten des C,-Atoms [42], was rnit den strukturellen Effekten der alternativen Richtungen (Gleichung (13) …”

Section: Isomerisationunclassified

Das Mehrzentrenproblem bei ionischen Polymerisationsprozessen

Erussalimsky¹

1983

Acta Polymerica

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Die gleichzeitige Wirkung verschiedener aktiver Zentren in ionischen Systemen wird sowohl unter dem Aspekt ihrer Besonderheiten als auch hinsichtlich ihres relativen Anteils an experimentellen Gesamteffekten betrachtet. Bildungsweise und konkrete Typen von koexistierenden aktiven Zentren in anionischen, kationischen und durch Übergangsmetallderivate initiierten Polymerisationsprozessen werden diskutiert. An Beispielen der Aggregierung, Dissoziation, Isomerisation, intermolekularen und intramolekularen Komplexbildung werden die Mehrzentreneffekte besprochen.

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Section: Isomerisationunclassified

Das Mehrzentrenproblem bei ionischen Polymerisationsprozessen

Erussalimsky¹

1983

Acta Polymerica

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“…Among the metal-free polymerization, organoinitiated methyl methacrylate (MMA), an industrially important class of monomer, has a wide range of applications. Up to now, there are several approaches to achieve the polymerization of MMA, which include anionic polymerization, 7,8 radical polymerization, [9][10][11][12] group transfer polymerization (GTP), 13 coordination addition polymerization 14 and Lewis pair polymerization. 15 The anionic polymerization of MMA is a powerful but challenging topic, which features a high degree of complexity of initiation and propagation kinetics, frequent occurrence of side reactions and aggregation of active chain ends as well as the resulting equilibria between different types of aggregates and ion pairs.…”

Section: Introductionmentioning

confidence: 99%

Synthetic and mechanistic aspects of anionic polymerization of methyl methacrylate using tetrabutyl ammonium thioimidate

Zhang

Wang

2021

Journal of Polymer Science

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The tetrabutylammonium salts of ionic organo‐initiator containing N,N'‐diisopropylthiourea (TUA‐1) or N,N'‐diethylthiourea (TUA‐2) serve as inexpensive initiators for the anionic polymerization of methyl methacrylate (MMA) at room temperature. The molecular weights of obtained polymers are in the range of 1500–22,700 g mol−1 and the molecular weight distributions are fairly broad (Đ = 1.9–2.5) in optimized cases. The molar ratio of monomer to initiator can be achieved up to 800. Side‐reactions, for example, backbiting, transfer reactions result in the polymerization being a non‐living manner, thus leading to broad molecular weight distributions of the resulting polymers. The effects of counterion nature were also studied from the polymerization of MMA using TUA‐1 anion with sodium or potassium salts as counterions under identical conditions. Detailed investigation indicates that the polymerization proceeds via a sulfur anion initiated repeated 1,4‐Machael addition. In general, thioimidate initiators induced MMA polymerization feature certain induction periods, which is ascribed to slow addition thioimidate to CC double bond of MMA as a result of low initiator efficiency.

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“…Side reactions involving nucleophilic attack at the ester group render anionic (meth)acrylate polymerization nonliving under typical conditions (11)(12)(13)(14)(15). The most common process is intramolecular "backbiting" of the active endgroup to the ante penultimate ester unit of the polymer chain (Equation 1) (13,(16)(17)(18).…”

Section: Side Reactionsmentioning

confidence: 99%

The Organometallic Polymerization of (Meth)acrylates: An Overview

Boffa

2000

ACS Symposium Series

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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

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Anionic polymerization

Cited by 59 publications

References 239 publications

Das Mehrzentrenproblem bei ionischen Polymerisationsprozessen

Das Mehrzentrenproblem bei ionischen Polymerisationsprozessen

Synthetic and mechanistic aspects of anionic polymerization of methyl methacrylate using tetrabutyl ammonium thioimidate

The Organometallic Polymerization of (Meth)acrylates: An Overview

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