Telechele Oligomere, 1. Die Rhodium‐katalysierte Synthese von telechelen Oligobutadienen

Heitz, Walter; Arlt, K.; Mehnert, W.

doi:10.1002/macp.1976.021770531

Cited by 7 publications

References 1 publication

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Telechelic oligomers, 4. Synthesis of telechelic oligobutadienes by rh‐catalysis

Arlt

Heitz

1979

Makromol. Chem.

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Polymerisation of butadiene using different Rh‐compounds, specially Rh(NO3)3, in allyl alcohol results in oligobutadienes with carbonyl functionality of 1 and hydroxyl functionality between 0—1. Under proper conditions telechelics are formed. Catalysis by Rh(NO3)3 can be accelerated by the addition of alcoholate or phosphine. The oligomers have exclusively 1,4‐trans‐structure. The combined use of alcoholate and triphenylphosphine results in oligobutadienes with 40% 1,4‐cis‐, 35% 1,4‐trans‐ and 25% 1,2 structure. Determination of the structure of isolated oligomers shows that both functional groups are incorporated by insertion of a complete allyl alcohol unit. According to the frequently found endgroup CH2C(CH2OH) … the incorporation of the hydroxyl group in the termination reaction by β‐hydride transfer is most likely. The carbonyl functionality is formed in the initiation step by hydride transfer from allyl alcohol to Rh. Analogous use of allyl chloride or allyl bromide results in telechelic oligobutadienes containing two halogens per molecule. but the structure of isolated oligomers shows that only one allyl halogenide unit is incorporated. The second terminal halogen is fixed to a butadiene unit. Again the characteristic group CH2C(CH2Cl)—… is found, suggesting a termination by β‐hydride transfer.

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Telechelic oligomers, 4. Synthesis of telechelic oligobutadienes by rh‐catalysis

Arlt

Heitz

1979

Makromol. Chem.

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Determination of the cumulative degree of polymerization for the dead‐end polymerization of styrene

David

Boutevin

Robin

2002

J. Polym. Sci. A Polym. Chem.

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This article explores the use of a new relation correcting theoretical (DPn) with experimental values obtained in the dead-end polymerization of styrene with azocompound. The syntheses were realized for several starting initiator-to-monomer ratios (C 0 's); values comprised between 10 and 0.1%, and the experimental (DPn) were obtained by size exclusion chromatography. Concerning the theoretical (DPn), a new relation is proposed considering the loss of initiating radicals [I ⅐ ] used in primary termination and both stationary states of I ⅐ and M ⅐ (macromolecular radicals) introduced as Bamford. Finally, (DPn) cum , previously defined by us, is introduced to consider the monomer conversion during oligomerization. Our relation fit very well in a large range of C 0 's, contrary to the application of the usual Mayo rule, and a discussion of validity is proposed. Our model also allows the prediction of (DPn) cum in a large range of telechelic oligomers from 10 to 150.

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Telechelic oligomers by radical reactions

Boutevin

Advances in Polymer Science

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Telechele Oligomere, 1. Die Rhodium‐katalysierte Synthese von telechelen Oligobutadienen

Cited by 7 publications

References 1 publication

Telechelic oligomers, 4. Synthesis of telechelic oligobutadienes by rh‐catalysis

Telechelic oligomers, 4. Synthesis of telechelic oligobutadienes by rh‐catalysis

Determination of the cumulative degree of polymerization for the dead‐end polymerization of styrene

Telechelic oligomers by radical reactions

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