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  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polydienes modified by a reaction coupled with hydroboration contain residual, highly reactive trialkylborane structures making these products instable in air. In the case of cyanomethylated polydienes obtained by this way, elimination of the residual trialkylborane structures by a selective, specific, and quantitative method was investigated: optimation of the cyanomethylation reaction did not result in a quantitative elimination and the acetolysis was found under various conditions not be to quantitative or specific, whereas alcaline oxidation reaction could be shown to be specific and quantitative but not completely selective: it induces, with low yields, a secondary hydrolysis reaction of the cyanomethylated structures. The products obtained by this last method and their acetylated and reduced derivatives were characterized by spectrographic analysis (IR and NMR).
    Notes: L'existence de structures trialkylboranes résiduelles dans les polydiènes modifiés par réaction couplée à l'hydroboration confère aux produits obtenus une instabilité résultant de la réactivité de ces structures à l'air. Pour les polydiènes cyanométhylés par cette voie, une méthode d'élimination des structures trialkylboranes par une réaction sélective, spécifique et quantitative a été recherchée: l'optimisation de la réaction de cyanométhylation n'a pas permis une élimination quantitative; l'acétolyse est, selon les conditions, non quantitative ou non spécifique tandis que la réaction d'oxydation alcaline s'est révélée spécifique et quantitative mais non totalement sélective: elle provoque simultanément et à de faibles taux l'hydrolyse parasite des structures cyanométhylées. La caractérisation des produits obtenus par cette dernière methode a été réalisée par analyse spectrographique (IR et NMR) des produits eux-měmes, de leurs dérivés acétylés et de leurs dérivés réduits.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Katalysatoren des ZIEGLER-NATTA-Typs wurden bei der Synthese von Blockcopolymeren aus Olefinen angewendet. Vor kurzem wurden Blockcopolymere aus Olefinen und Vinylmonomeren hergestellt, wobei die aus der anionischen Polymerisation stammenden „lebenden“ Enden in freie Radikale überführt wurden, die dann die Polymerisation der Vinylmonomeren starten.Die Ausbeute an Blockcopolymeren überschreitet jedoch kaum einige Prozent, da bekanntlich die Anzahl „lebender“ Ketten sehr gering ist. Es wurde gefunden, daß das Zufügen eines passenden Kettenüberträgers wie Zinkdiäthyl während der koordinativen Polymerisation die Anzahl der „aktiven“ Zentren, die fähig sind, in Gegenwart von radikalischen Initiatoren die Polymerisation der Vinylmonomeren zu initiieren, beträchtlich erhöht. Dieser neue Weg ermöglicht hohe Ausbeuten von Blockcopolymeren mit unterschiedlichem Vinylmonomerengehalt. Außerdem ist es möglich, unter gewissen Bedingungen entweder Block- oder Block- und Pfropf- oder sogar ausschließlich Pfropfcopolymere herzustellen.Die Bildung der entsprechenden Homopolymeren kann weitgehend verhindert werden. Als Beispiel dieser neuen Technik wird hier nur die Synthese von Polyäthylen/Polymethylmethacrylat Block- und/oder Pfropfcopolymeren beschrieben, obschon eine ganze Reihe anderer Copolymerer untersucht wurde.
    Notes: Catalysts of the ZIEGLER-NATTA type have been applied widely for the synthesis of olefin block copolymers. More recently the preparation of olefin block polymers with vinyl monomers has been achieved by converting the “living” chains from an anionic polymerization into free radicals in the presence of peroxides to allow the formation of blocks. The yield of block copolymers does not exceed a few per cent since it is well known now that the number of “living” chains is extremely low. It has been found that the incorporation of a suitable chain transfer agent such as diethyl zinc during the coordinative polymerization provides a new way to increase considerably the “active” centers which are capable to initiate, in the presence of a radical initiator, the polymerization of the vinyl monomers giving high yield of block copolymers containing variable amounts of the vinyl polymers. Moreover, under certain conditions, it is possible to synthesize either block, or block and graft, or graft copolymers only. The formation of the corresponding homopolymers can be avoided to a large extent. In order to illustrate this new technique with an example, we describe here only the synthesis of polyethylene/polymethylmethacrylate, block and/or graft copolymers, although-a-large variety of other copolymers has been studied.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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