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Journal ArticleDOI

No Catalyst Copolymerization by Spontaneous Initiation Mechanism

01 Jan 1976-Pure and Applied Chemistry (International Union of Pure and Applied Chemistry)-Vol. 48, Iss: 3, pp 307-315
TL;DR: In this article, a new type of copolymerization, which requires no added initiator, is presented, and a survey of elemental reactions of selected combinations of Copolymerisation is given.
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.
Citations
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01 Jan 1983
TL;DR: In this paper, a review of the kinetics and mechanisms of anionic polymerization is presented, and the results of such studies are compared with those derived from investigations of radical-anions, carbanions and other ionic species.
Abstract: Following a short introduction and a brief discussion of thermodynamics of propagation, the kinetics and mechanisms of anionic polymerization are reviewed. The systems involving living polymers, a term introduced by this writer, are discussed in greater detail because the existence of various ionic species participating in polymerization was clearly revealed by their studies. Indeed, a large part of this review is concerned with the methods used in identification of these species and determination of their role in various polymerizing systems. The results of such studies are compared with those derived from investigations of radical-anions, carbanions and other ionic species.

44 citations

Journal ArticleDOI
TL;DR: In this paper, various copolyesteramides were prepared by melt compounding at 220 °C involving reaction of poly(styrene-co-maleic anhydride), SMA, with 6, 17, and 28 wt % maleic anoxide content, and 1-dodecanol, C12OH, in the presence of 2-undecyl-1,3-oxazoline, C11OXA.
Abstract: Various copolyesteramides were prepared by melt compounding at 220 °C involving reaction of poly(styrene-co-maleic anhydride), SMA, with 6, 17, and 28 wt % maleic anhydride content, and 1-dodecanol, C12OH, in the presence of 2-undecyl-1,3-oxazoline, C11OXA. Copolymer architectures were examined by means of 1H NMR, FTIR, DSC, and TGA using model compounds prepared via solution reactions. While conversion of anhydride with alcohol was poor due to the thermodynamically favored anhydride ring formation, very high conversions were achieved when stoichiometric amounts of C11OXA were added. According to spectroscopic studies esteramide groups resulted from reaction of oxazoline with carboxylic acid intermediate. In the absence of alcohol, C11OXA reacted with anhydride to produce esterimides. Effective attachment of flexible n-alkyl side chains via simultaneous reaction of C12OH and C11OXA resulted in lower glass-transition temperatures of copolyesteramides. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1222–1231, 2000

30 citations

Journal ArticleDOI
TL;DR: In this article, copolymers of 2-ethyl-2-oxazoline (ETOX) and N-phenylmaleimide (PhMI) without initiator were prepared at different feed mole ratios, solvents, temperatures and times.
Abstract: Copolymers of 2-ethyl-2-oxazoline (ETOX) and N-phenylmaleimide(PhMI) without initiator were prepared at different feed mole ratios, solvents, temperatures and times. The copolymers are almost statistical and rich in N-phenylmaleimide. The copolymer composition was determined by 1H NMR.

29 citations

Journal ArticleDOI
TL;DR: In this article, copolymers of 2-ethyl-2-oxazoline with acrylic acid were synthesized without an initiator at 70°C in acetonitrile.

20 citations

Journal ArticleDOI
Takeo Saegusa1
TL;DR: In this article, a new Copolymerisationstyp beschrieben, der sich dadurch auszeichnet, das das Kettenwachstum spontan ohne Zusatz eines Katalysators ablauft.
Abstract: In diesem Aufsatz wird ein neuer Copolymerisationstyp beschrieben, der sich dadurch auszeichnet, das das Kettenwachstum spontan ohne Zusatz eines Katalysators ablauft. Ein nucleophiles (MN) und ein elektrophiles Monomer (ME) reagieren zu einem Zwitterion (+MNM), von dem Start- und Wachstumsreaktionen ausgehen. 23 neuartige Copolymerisationen wurden auf der Basis dieses Konzepts ausgearbeitet. Als MN-Monomere wurden funf- und sechsgliedrige cyclische Iminoether, Dihydro-2(3H)-furanimin, ein Azetidin, ein cyclischer Phosphinsaureester und eine Schiff-Base untersucht, als ME-Monomere β-Propiolacton, ein cyclisches Dicarbonsaureanhydrid, ein Sulton, Acrylsaure, Acrylamid, ein β-Hydroxyalkylarylat und Ethylensulfonamid. Bei den meisten Kombinationen entstehen alternierende 1 : 1-Copolymere. Auserdem wurde die alternierende 1 : 1-Copolymerisation eines cyclischen Phosphits mit α-Ketosauren entdeckt.

19 citations

References
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Journal ArticleDOI
Takeo Saegusa1
TL;DR: In this article, a new Copolymerisationstyp beschrieben, der sich dadurch auszeichnet, das das Kettenwachstum spontan ohne Zusatz eines Katalysators ablauft.
Abstract: In diesem Aufsatz wird ein neuer Copolymerisationstyp beschrieben, der sich dadurch auszeichnet, das das Kettenwachstum spontan ohne Zusatz eines Katalysators ablauft. Ein nucleophiles (MN) und ein elektrophiles Monomer (ME) reagieren zu einem Zwitterion (+MNM), von dem Start- und Wachstumsreaktionen ausgehen. 23 neuartige Copolymerisationen wurden auf der Basis dieses Konzepts ausgearbeitet. Als MN-Monomere wurden funf- und sechsgliedrige cyclische Iminoether, Dihydro-2(3H)-furanimin, ein Azetidin, ein cyclischer Phosphinsaureester und eine Schiff-Base untersucht, als ME-Monomere β-Propiolacton, ein cyclisches Dicarbonsaureanhydrid, ein Sulton, Acrylsaure, Acrylamid, ein β-Hydroxyalkylarylat und Ethylensulfonamid. Bei den meisten Kombinationen entstehen alternierende 1 : 1-Copolymere. Auserdem wurde die alternierende 1 : 1-Copolymerisation eines cyclischen Phosphits mit α-Ketosauren entdeckt.

19 citations