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Journal ArticleDOI

Alternating copolymerisations of dioxaphospholane and dioxaphosphorinane with γ-butyrolactone and ethylene oxide

01 Jan 1982-European Polymer Journal (Pergamon)-Vol. 18, Iss: 9, pp 803-807
Abstract: Alternating copolymers containing phosphorus were prepared from 2-phenyl-1,3,2-dioxaphospholane, 2-phenyl-4-oxo-5,6-benzo-1,3,2-dioxaphosphorinane with ethylene oxide and γ-butyrolactone. The polymerisations took place without added catalyst. The copolymers were characterised by i.r. and NMR spectroscopy, viscosity measurements and phosphorus estimation. Key intermediates responsible for initiation and propagation of the copolymerisations were isolated and the mechanism of copolymerisation is discussed.

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Topics: Ethylene oxide (55%)
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Journal ArticleDOI
TL;DR: The overall results indicate that the lack of polymerizability of gamma-butyrolactone should be attributed to the low strain of the ring, which shows much less geometric distortion in the ester group than delta-valerolactone, and the notable stability of the coiled conformations found in model compounds of poly-4-hydroxybutyrate.

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Abstract: γ-Butyrolactone, unlike δ-valerolactone, does not polymerize despite a strain energy of ∼8 kcal mol-1 which could be relieved by opening the s-cis lactone ester bond to an s-trans ester bond in the polymer. To explain this anomaly, we have applied quantum mechanical methods to study the thermochemistry involved in the ring-opening reactions of γ-butyrolactone and δ-valerolactone, the conformational preferences of model molecules that mimic their corresponding homopolyesters, and the variation of enthalpy associated to the polymerizability of such two cyclic lactones. The overall results indicate that the lack of polymerizability of γ-butyrolactone should be attributed to the low strain of the ring, which shows much less geometric distortion in the ester group than δ-valerolactone, and the notable stability of the coiled conformations found in model compounds of poly-4-hydroxybutyrate.

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129 citations


Journal ArticleDOI
Abstract: The spontaneous zwitterionic copolymerisation (SZWIP) of compatible nucleophilic and electrophilic monomers is a relatively unknown and unexplored method for the synthesis of (predominantly alternating) degradable co- and terpolymers. A wide range of monomers allows for the synthesis of different polymer classes with various functionalities, including poly(aminoester)s, poly(ester amide)s and poly(phosphoester)s. In this review, we discuss this undervalued copolymerisation method and its potential for the facile preparation of functional polymeric systems. In this context, the polymers synthesised to date by SZWIP as well as recent insights into this polymerisation technique are highlighted. Post-polymerisation modifications and applications of polymers obtained by SZWIP are also discussed.

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10 citations


Journal ArticleDOI
Abstract: The peculiarities of the reactions of 2-R-benzo[d]-1,3,2-dioxaphosphorin-4-ones, 2-R-naphtho[d]-1,3,2-dioxaphosphorin-4-ones, 2-R-8-azabenzo[e]-1,3,2-dioxaphosphorin-4-ones, and 2-R-1,3,2-dioxaphospholan-4-ones with unsaturated compounds are summarized in the review. The reactions proceed in the mild conditions and lead to the formation of the seven- and six-membered heterocycles 1,3,2-dioxa-, 1,3,2-oxaza-, 1,4,2-dioxa-, and 1,4,2-oxazaphosphepines and 1,3,2- and 1,4,2-dioxaphosphorinanes with a high regio- and stereoselectivity. The hydrolysis and thermolysis of the some benzophosphepine derivatives leads to the substituted fluorinated ketones and various nonphosphorus heterocycles.

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3 citations


References
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Journal ArticleDOI
Abstract: A new type of copolymerization is presented here, which requires no added initiator. A zwitterion 1 is generated by the interaction between two monomers; one monomer has nucleophilic reactivity (MN) and the other possesses electrophilic reactivity (ME). Two moles of the genetic zwitterion 1 react with each other to produce a dimeric zwitterion 2. The dimeric zwitterion 2 grows by its reaction with 1 to polymeric zwitterion 3. Intermolecular reaction of macro-zwitterions (dimeric 2 and polymeric 3) also occurs, which brings about a sharp increase in molecular weight. In a series of studies, six MN monomers and six ME monomers have been investigated. As the MN monomer, cyclic imino ether, exo-imino cyclic ether, azetidine, Schiff base and cyclic phosphonite have been selected. As the ME monomer, lactone, cyclic anhydride, sultone (sulfolactone), acrylic acid, acrylamide and β-hydroxyethyl acrylate have been successfully used. Thus, thirty-six combinations (six times six) of copolymerization have now become conceivable. The present paper gives a survey of elemental reactions of selected combinations of copolymerization. The emphasis is laid on the discussions of recent results.

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37 citations



Journal ArticleDOI
Abstract: A new type of copolymerization is presented which proceeds without any added catalyst A monomer of nucleophilic reactivity (MN) is mixed with the second monomer having electrophilic reactivity (ME) to produce a zwitterion +MN—ME-(1), which is responsible for initiation as well as propagation By the following scheme of reactions, alternating copolymer is formed Sometimes the reactions between zwitterion species 1, 2, and 3 with free monomer occur, which give rise to the formation of copolymer having a biased composition Cyclic imino ethers, exoimino cyclic ether, and azetidine have been explored as the MN comonomers β-Propiolactone, cyclic anhydride, sultone (sulfolactone), acrylic acid, acrylamide, and β-hydroxyethyl acrylate have successfully been adopted as the ME comonomers Copolymerization occurred without any catalyst with all combinations of MN and ME monomers, and various alternating copolymers were produced Several important results which explicate the new concept are presented and

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29 citations