Poly(macromonomers): Homo- and Copolymerization

Ito, Koichi; Kawaguchi, Seigou

doi:10.1007/3-540-68310-0_3

Cited by 160 publications

(158 citation statements)

References 134 publications

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“…Although there is not yet an agreement in the literature on the relative importance of these factors, it appears from a number of monomer reactivity ratios reported so far [18,19], that the nature of the polymerizing end-groups largely determines the reactivity of macromonomers in copolymerization with a conventional monomer and that other factors are usually of less importance. In fact, model monomers for the end group can provide a useful first approximation to the reactivity of a given macromonomer.…”

Section: Model Monomer Estimationmentioning

confidence: 89%

Radical copolymerization studies of an amphiphilic macromonomer derived from Triton X-100. Reactivity ratios determination by in situ quantitative 1H NMR monitoring

Larraz

Elvira

Gallardo

et al. 2005

Polymer

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Section: Model Monomer Estimationmentioning

confidence: 89%

Radical copolymerization studies of an amphiphilic macromonomer derived from Triton X-100. Reactivity ratios determination by in situ quantitative 1H NMR monitoring

Larraz

Elvira

Gallardo

et al. 2005

Polymer

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“…This phenomenon is known in literature for brushor bottlebrush-type polymers synthesized by a macromonomer approach. [40] In this case, the T g is predominantly determined by the excess free volume effect of endgroup per unit MW. Generally, T g was found to decrease with decrease in the molecular weight of the macromonomer and also that of polymacromonomers.…”

Section: ½H ¼ Km Amentioning

confidence: 99%

Branched and Functionalized Polybutadienes by a Facile Two‐Step Synthesis

Wurm

López-Villanueva

Frey

2008

Macro Chemistry & Physics

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Anionic polymerization was used to prepare silane‐endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9 000 to 34 000 g · mol−1. These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB2 + A type “pseudocopolymerization” method. All branched polymers were analyzed by SEC, SEC‐MALLS, SEC‐viscosimetry. 1H NMR spectroscopy, and DSC concerning their branching ratio. The branching parameters for the branched polymers exhibited similar characteristics as for hyperbranched polymers obtained from conventional AB2 monomers. Detailed kinetic studies showed that the polymerization occurred very rapidly in comparison to the hydrosilylation polymerization of classical AB2 type carbosilane monomers.magnified image

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“…The same reaction sequence was repeated to afford the target exact graft copolymer having two branch chains. In this case, three reaction steps are employed in an iterative synthetic sequence: The poly(macromonomer) that becomes accessible by the living polymerization of well-defined macromonomers is one of the ultimate graft copolymers, carrying one branch on each repeating unit [232]. In this case, three reaction steps are employed in each iterative synthetic sequence: 1) A transformation reaction to convert the α-terminal SiOP group into a 3-bromopropyl function.…”

Section: Graft Copolymersmentioning

confidence: 99%

Anionic Polymerization: Recent Advances

Ishizone

Hirao

2012

Materials Science and Technology

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polymerize the monomers in classes B, C, and D, but they cannot initiate the polymerization of monomers in class A. The initiators in class c can polymerize both C and D class monomers, while they are inert for the monomers in classes A and B. The least-reactive initiators in class d, such as amines and phosphines, undergo anionic polymerization of the most-reactive D class monomers Among the monomers, α-cyanoacrylate is polymerized, even with water.The relationship between a monomer and its growing chain-end anion is also important in order to understand anionic polymerization behavior. In general, the most-reactive chain-end anions derive from the least-reactive monomers and vice-versa, because they are conjugated bases and acids with each other. For example, when considering styrene (class A) and methyl methacrylate (MMA) (class B), the latter is more reactive than the former because the electron density on the C=C bond of MMA is considerably reduced by the electron-withdrawing ester carbonyl group, whereas that on the styrene C=C bond is influenced much less by the phenyl group. On the other hand, the chain-end anion derived from MMA is also reduced in electron density by the same electron-withdrawing effect, and becomes less reactive than that derived from styrene. In practice, the chain-end anion from MMA has no ability to polymerize styrene, whilst the chain-end anion from styrene can polymerize styrene and, of course, the more-reactive MMA. Thus, the monomers in class A will always produce the most reactive growing chain-end anions that can polymerize all monomers in classes A, B, C, and D. In contrast, the least-reactive chain-end anions derived from the most-reactive monomers in class D can polymerize only the monomers in class D. These relationships are very important -even critical -for selecting the correct anionic initiator in polymerization, as well as when synthesizing block copolymers.

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Poly(macromonomers): Homo- and Copolymerization

Cited by 160 publications

References 134 publications

Radical copolymerization studies of an amphiphilic macromonomer derived from Triton X-100. Reactivity ratios determination by in situ quantitative 1H NMR monitoring

Radical copolymerization studies of an amphiphilic macromonomer derived from Triton X-100. Reactivity ratios determination by in situ quantitative 1H NMR monitoring

Branched and Functionalized Polybutadienes by a Facile Two‐Step Synthesis

Anionic Polymerization: Recent Advances

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