Synthesis of Well‐Defined Poly(meth)acrylamides with Varied Stereoregularity by Living Anionic Polymerization

Ishizone, Takashi

doi:10.1002/9780470825150.ch14

Cited by 1 publication

(2 citation statements)

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“…Nevertheless, it should be emphasized again that even the low nucleophilic Grignard reagent and alkoxide anion could initiate the polymerization of this particular hydrocarbon monomer, BF. This strongly supports the fact that BF is categorized as a new class of hydrocarbon monomers from the viewpoint of anionic polymerizability. , …”

Section: Resultssupporting

confidence: 78%

“…These living polymerization systems also allow the syntheses of tailored block copolymers by the sequential copolymerization and end-functionalized polymers by the suitable termination reactions. Although the propagating carbanions derived from the hydrocarbon monomers show extremely high nucleophilicities, the anionic polymerizability of hydrocarbon monomers is significantly lower than those of polar monomers including vinylpyridines, (meth)acrylates, and N , N -dialkylacrylamides. , Typical strong anionic initiators, such as sec -butyllithium ( sec -BuLi) and potassium naphthalenide (K-Naph), are necessary to quantitatively initiate the polymerization of hydrocarbon monomers. It is noteworthy that the range of the hydrocarbon monomers capable of the living anionic polymerization is still limited regardless of the recent progress of this research field.…”

Section: Introductionmentioning

confidence: 99%

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High Anionic Polymerizability of Benzofulvene: New Exo-Methylene Hydrocarbon Monomer

et al. 2015

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The anionic polymerization of benzofulvene (BF) quantitatively proceeded with various initiators, such as secBuLi, diphenylmethyllithium, diphenylmethylpotassium, triphenylmethyllithium, and triphenylmethylpotassium, in THF at −78°C to give polymers having predicted molecular weights based on the molar ratios between BF and the initiators and narrow molecular weight distributions (MWD, M w /M n < 1.1). Although the initiation efficiencies were not quantitative, BF could also be polymerized with benzylmagnesium chloride, potassium tert-butoxide, and the anionic living poly(tert-butyl methacrylate), indicating the high anionic polymerizability. The planar conformation and the polarized electron density of BF obtained by the density functional theory (DFT) calculation supported the observed anionic polymerizability higher than that of 2-phenyl-1,3-butadiene, the acyclic analogue of BF. A series of new block copolymers, polystyrene-b-poly(BF), poly(2-vinylpyridine)-bpoly(BF), and poly(tert-butyl methacrylate)-b-poly(BF), were synthesized by the sequential anionic copolymerization of BF and the comonomers. On the other hand, no polymerization of styrene and 2-vinylpyridine took place with the living poly(BF), indicating the low nucleophilicity of the propagating indenyl anion formed from BF. BF readily underwent the free-radical polymerization with α,α′-azobis(isobutyronitrile), while the observed cationic polymerizability of BF was quite low. 1 H and 13 C NMR analyses revealed that the repeating units of poly(BF) consisted of a 1,2-addition unit and a 1,4-addition unit without a 3,4-addition unit regardless of the polymerization conditions. The exo-methylene moiety (CH 2 ) of BF always participated in the addition polymerization. The addition modes were dependent on the polymerization temperature and not on the solvent or the countercation of the anionic initiator. For instance, polymer obtained with sec-BuLi in THF at 40°C contained 72% of the 1,4-addition unit and 28% of the 1,2-addition unit. Therefore, BF acted as a polymerizable 1,3-diene possessing a fixed transoid framework.

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Section: Resultssupporting

confidence: 78%

Section: Introductionmentioning

confidence: 99%