Anionic polymerization of methacrylate esters initiated with esters of α‐metallocarboxylic acids

Lochmann, L.; Rodová, Miroslava; Trekoval, J.

doi:10.1002/pol.1974.170120924

Cited by 57 publications

(17 citation statements)

References 5 publications

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“…Diphenylethylene (DPE, Aldrich) was titrated with a small amount of BuLi and distilled under high vacuum. Ethyl a-lithioisobutyrate (EIBLi) was synthesized acording to Lochmann 44) . Octane was distilled over Na-K alloy and used as internal standard for GC.…”

Section: Methodsmentioning

confidence: 99%

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

Baskaran

Müller²

2000

Macromol. Rapid Commun.

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Section: Methodsmentioning

confidence: 99%

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

Baskaran

Müller²

2000

Macromol. Rapid Commun.

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“…The really efficient ligands discovered to date in this field may be classified into three groups, the structure of the most representative ones being shown in Scheme 2: 1. µ-type ligands, that form polycentric bonding with the metal ester enolate: metal alkoxides [38][39][40][41][42], aluminum alkyls [43][44][45], and inorganic salts [46][47][48][49]. 2. σ-type ligands, that form coordinative complexes with the metal counterion of the active species: crown ethers [50] and kryptands [51].…”

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

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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.

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“…2, 1976 polymerization carried out at ambient temperature. 9 In the polymerization with monofunctional alkoxides no cross-linked polymer was formed, as had been expected, but the graft reaction was found to proceed. Unfortunately, in the present stage a "pure" block copolymer was not obtained by our polymerizations with alkoxides derived from PEO.…”

Section: Discussionmentioning

confidence: 56%

Polymerization of Methyl and Ethyl Methacrylates Initiated with Alkali-Metal Alkoxide Derivatives of Poly(ethylene oxide)

Tomoi

Shibayama

Kakiuchi

1976

Polym J

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ABSTRACT:The polymerization of methacrylates with alkali-metal alkoxide derivatives of poly( ethylene oxide) (PEO) yielded copolymers which consisted of PEO and polymethacrylates containing block and graft units. The block copolymerization was initiated by addition of the alkoxide to the carbon-carbon double bond of methacrylates, and the graft reaction onto the block copolymer formed was thought to proceed by transesterification between the pendant ester groups of the copolymer and the unreacted alkoxide. The grafting of the alkoxide derivative of PEO having two terminal hydroxyl groups resulted in formation of cross-linked copolymers, while the polymerization with the alkoxide having one active end gave soluble copolymers. The relative amount of the grafted ester groups in the copolymers was estimated by NMR spectroscopy.KEY WORDS Anionic Polymerization I Block Copolymer I Graft Copolymer I Poly(ethylene oxide) I Alkyl Methacrylate 1 Alkali-Metal Alkoxide I Crosslinking I Transesterification 1In a previous paper/ it was shown that the polymerization of methyl methacrylate (MMA) with alkali-metal salts of 2-substituted ethanols such as 2-methoxyethanol and 2-dimethylaminoethanol proceeded easily in the presence of hexamethylphosphoramide (HMPA).In this paper, the polymerization of MMA and ethyl methacrylate (EMA) with alkali-metal alkoxide derivatives of poly(ethylene oxide) (PEO) has been investigated, since the formation of block copolymers, poly( ethylene oxide-b-methacrylates), was expected from the similarity of structure between 2-methoxyethanol and the PEO carrying terminal hydroxyl groups. The block or graft copolymers composed of polymers having different properties, e.g., rubbery and glassy or hydrophilic and hydrophobic, have been noted as a kind of new prospective polymer materials. 2 PEO has hydrophilic and rather rubbery properties, while polymethacrylates have hydrophobic and glassy ones. For example, poly(methyl methacrylate-g-ethylene oxide) have already been synthesized by the grafting of alkoxide derivatives of PEO onto poly(methyl methacrylate)."In this study, the synthesis of poly(ethylene oxide-b-methacrylates) was attempted by means of the anionic polymerization of vinyl monomers 190 (MMA and EMA) with macromolecular initiators (alkoxide derivatives of PEO). Such block copolymers, which consist of alkylene oxide and vinyl or diene monomers, have already been synthesized by radical copolymerization, 4 but not by anionic polymerization. EXPERIMENTAL ReagentsTetrahydrofuran (THF) was distilled over metallic sodium under a nitrogen atmosphere. HMPA was refluxed and distilled over calcium hydride in vacuo. PEO having terminal hydroxyl groups was dried by azeotropic 'distillation in toluene. 3 2-Methoxyethanol was refluxed and distilled over calcium hydride under a nitrogen atmosphere. Ethylene oxide (Nippon Shokubai Kagaku) was used without further purification. MMA and EMA were purified by conventional methods, refluxed, and distilled over calcium hydride under vacuum just before use. Sodium ...

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Anionic polymerization of methacrylate esters initiated with esters of α‐metallocarboxylic acids

Cited by 57 publications

References 5 publications

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

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

Anionic polymerization of methacrylic monomers: characterization of the propagating species

Polymerization of Methyl and Ethyl Methacrylates Initiated with Alkali-Metal Alkoxide Derivatives of Poly(ethylene oxide)

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