Equilibrium anionic polymerization of β‐methoxypropionaldehyde

Hashimoto, Kazuhiko; Sumitomo, Hiroshi; Ohsawa, Shinji

doi:10.1002/pol.1975.170131212

Cited by 9 publications

(3 citation statements)

References 28 publications

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“…MCPA that contains an ester group seems to polymerize faster than ether-substituted aldehydes and the corresponding unsubstituted aliphatic aldehydes reported in earlier articles. [26][27][28] For the isolation of the resulting polymer volatile compounds in the polymerization system were distilled away in vacuo after the termination and the initiator residue was filtered out. The residual viscous oil was poly(P-methoxycarbonylethyl)oxymethylene, structurally identical with that produced by the polymerization of MCPA with organoaluminum compounds21 in spite of the different shapes.…”

Section: Resultsmentioning

confidence: 99%

“…Tetrahydrofuran(THF) and acetic anhydride were purified by the same methods as described in a previous paper. 24 The benzophenone-monolithi_um complex(Li-BzPh) solution in THF was prepared by mixing an equimolar amount ofbenzophenone with the benzophenone-dilithium complex-THF solution, which was previously produced quarititatively by the addition of benzophenone-THF solution to an excess of lithium metal at 0°C. 24 · 28 …”

Section: Methodsmentioning

confidence: 99%

“…A benzophenone-monolithium complex (Li-BzPh)-THF solution (0.05 moleAiter) was obtained by mixing an equimolar amount of benzophenone with the benzophenone-dilithium complex in THF prepared quantitatively by the addition of the benzophenone-THF solution to an excess of lithium metal at 0°C (ref. 26).…”

Section: Methodsmentioning

confidence: 99%

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Equilibrium Anionic Polymerization of Hexanal

Hashimoto

Sumitomo

1979

Polym J

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KEY WORDSEquilibrium Anionic Polymerization / Hexanal / Aliphatic Aldehydes / Thermodynamic Parameter / Substituent Effect / Early investigations on the polymerization of aldehydes have been comprehensively summarized in several articles. 1 -4 Most of the pioneering thermodynamic studies were related to the equilibrium polymerization of formaldehyde and haloaldehydes under different experimental conditions. 5 -20 For more quantitative understanding of their polymerizability, the thermodynamic parameters determined under the same conditions should be compared, because these are known to depend upon phase states in monomer and polymer, initial monomer concentration, kind of solvent, temperature range, and so on. 21 On the other hand, the improvements of high vacuum technique and the ingenious choice of the polymerization conditions have enabled the equilibrium anionic polymerization of aliphatic aldehydes containing ()(-hydrogens to be performed without simultaneous side reactions such as aldol condensation. 14 • 22 -27 In the present study the equilibrium anionic polymerization of hexanal (O=CHCH 2 CH 2 CH 2 CH 2 CH3 , HA) has been achieved and compared with those of other aliphatic aldehydes 25 · 27 in order to estimate the effects of nalkyl groups on the polymerization of aldehydes.EXPERIMENT AL All procedures, including purification of materials, preparation of initiator, and polymerization, were carried out in a high-vacuum system. 24 • 28 MaterialsCommercially available hexanal (HA) was purified by rectification in an atmosphere of dry nitrogen through a packed column placed in an adiabatic vacuum glass cylinder (the number of the theoretical plates, ca. 60). The main fraction was distilled again in vacuo after drying over molecular sieves. Tetrahydrofuran(THF) and acetic anhydride were purified by the same methods as described in a previous paper. 24 The benzophenone-monolithi_um complex(Li-BzPh) solution in THF was prepared by mixing an equimolar amount ofbenzophenone with the benzophenone-dilithium complex-THF solution, which was previously produced quarititatively by the addition of benzophenone-THF solution to an excess of lithium metal at 0°C. 24 · 28 PolymerizationA THF solution of HA (2 mo! I -i) was prepared and subdivided into 5 ml portions in a high vacuum. The initiator solution (0.05 mo! I -1 ) containing ca. 0.12 mmol of Li-BzPh complex was diluted with the required amount ofTHF, which was calculated so as to give the desired initial concentrations of the initiator and the monomer at the applied polymerization temperature. In order to avoid possible side reactions such as aldol condensation, especially during the initiation step; 2 -24 the THF solution of HA was poured into Li-BzPh solution under vigorous stirring at a temperature below -78°C. After the solution was kept at a constant temperature for a desired time, a large amount of acetic anhydride (3-4 ml) was added to the solution in order to terminate the reaction at the polymerization temperature; then the solution was allowed to stan...

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Equilibrium Anionic Polymerization of Hexanal

Hashimoto

Sumitomo

1979

Polym J

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Heats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer Concentrations, and Polymerizability of Heterocyclic Compounds

Léonard

1999

The Wiley Database of Polymer Properties

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Equilibrium anionic polymerization of n‐valeraldehyde

Hashimoto

Sumitomo

Ohsawa

1976

J. Polym. Sci. Polym. Chem. Ed.

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This paper describes an anionic polymerization of n‐valeraldehyde (VA) in tetrahydrofuran (THF) initiated by benzophenone‐monolithium complex in a high vacuum system. In spite of the deposition of the resulting polymer an equilibrium state between the monomer and the polymer was observed at a temperature range of −90 to −68°C. From the linear relationship between the equilibrium monomer concentration and the polymerization temperature, values of −5.3 ± 0.3 kcal/mole and −25.7 ± 1.4 cal/mole‐deg, respectively, were evaluated for the enthalpy change and the entropy change in the present system. The effect of polar substituents on the polymerizability of aldehydes is discussed from the comparison of these values with those in the case of β‐methoxypropionaldehyde.

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Equilibrium anionic polymerization of β‐methoxypropionaldehyde

Cited by 9 publications

References 28 publications

Equilibrium Anionic Polymerization of Hexanal

Equilibrium Anionic Polymerization of Hexanal

Heats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer Concentrations, and Polymerizability of Heterocyclic Compounds

Equilibrium anionic polymerization of n‐valeraldehyde

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