Mechanism of alternating copolymerization of acrylic monomers with donor monomers in the presence of lewis acid

Hirai, Hidefumi

doi:10.1002/pol.1976.230110102

Cited by 116 publications

(35 citation statements)

References 85 publications

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“…Je nach System k6nnen die Gleichungen sehr verschieden aussehen [1]. Ferner gibt es ftir jeden der oben beschriebenen Mechanismen kinetische Untersuchungen, deren Ergebnisse mit den mechanistischen Vorstellungen vertr~iglich sind, so dat~ auch yon dieser Seite keine Entscheidung dariiber m6glich ist, welcher Mechanismus zutrifft.…”

Section: Kinetikunclassified

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Alternierende Copolymerisation von Styrol und Benzylmethacrylat in Gegenwart von Ethylaluminiumsesquichlorid

Braun¹,

Menzel²

1982

Colloid & Polymer Sci

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Abstract:The alternating copolymerization of styrene and benzylmethacrylate shows a different behaviour at the beginning of the reaction and later on. Thus the composition and the intrinsic viscosity of the products as well as the reaction rate become constant only after the initial stage. The lH-NMR-spectra of alternating and statistical copolymers with equal composition show distinct differences. The spectrum of the alternating copolymer confirms the alternating structure as well as an atactic chain configuration.

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Section: Kinetikunclassified

“…Dies ist in der Literatur fiir sehr viele verschiedene Donator/Akzeptor/Lewiss~iure-Kombinationen beschrieben (l~bersicht in [1]). Es besteht jedoch noch Uneinigkeit dariiber, nach welchem Mechanismus der alternierende Einbau der Comonomeren in die Kette stattfindet.…”

Section: Introductionunclassified

Alternierende Copolymerisation von Styrol und Benzylmethacrylat in Gegenwart von Ethylaluminiumsesquichlorid

Braun¹,

Menzel²

1982

Colloid & Polymer Sci

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“…Consequently, Nx and NY also equal the total number of substituents Y 1 and Y z, respectively. Then, (1) and (2) When the average number of Y 1 , statistically remaining unreacted following the intramolecular reaction of Y 1 with X on the sequence-i, is defined by S;, the total number of Y 1 statistically remaining unreacted, N,, is given by eq 3, N,= L S;P; (3) i=O and the ratio of Y 1 remaining unreacted to the total number of Y 1 in the original copolymer is given by R=N,/Nx= L S;PJL iP; (4) i=O i=O…”

Section: Definition Of the Theoretical Maximum Conversionmentioning

confidence: 99%

Intramolecular Reaction between Neighboring Substituents of Specially-Designed Alternating Copolymers

Hirabayashi

Yokota

1981

Polym J

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ABSTRACT:The maximum conversion of an intramolecular reaction between neighboring substituents on specially-designed alternating copolymers was calculated theoretically. The terpolymer of monomers A, D1, and D2 , were supposed to consist of two alternating units, A-D1 and A-D2, distributed in a certain statistical state. In such a modified alternating copolymer, substituent X on unit A was permitted to perform the intramolecular reaction only with substituent Y1 on unit D1, not with Y2 on D2 . As a result, the theoretical maximum conversion could be expressed as a function of a mole fraction of A-D1 . If these alternating units were arranged as alternatively as possible, the best conversion near to 100% could be achieved over a wide range of the A-D1 fraction. Even if the arrangement was random, a considerably good conversion beyond 86.5% could still be expected. However, the blocky arrangement resulted in limiting the yield to 86.5% (Flory's limit) which was equal to the statistically possible level in the simple alternating copolymer of A and D1.

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“…The trap-to-trap technique under reduced pressure ( 100 mmHg) was preferable as a purification method. bp 74-75°C (760 mmHg); NMR (CDC1 3 …”

Section: Monomersmentioning

confidence: 99%

“…Inevitably, 13.5% of the substituents remain unreacted, as was experimentally observed in Hirooka's study. 4 Alternating copolymers, whose syntheses have been developed in this decade, 3 have a favorable arrangement of two substituents for intramolecular reaction. Hirooka et a/.…”

mentioning

confidence: 99%

Ternary Copolymerization of Trimethylvinyloxysilane, Styrene, and Acrylic Esters Catalyzed by Organoaluminum Compounds

Hirabayashi

Yokota

1981

Polym J

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ABSTRACT:The ternary copolymerization of trimethylvinyloxysilane, styrene, and methyl or phenyl acrylate was attempted in the presence of organoaluminum compounds at 0°C. All copolymers had a considerable amount of five-membered lactone structures in their backbone chains following the hydrolysis of the trimethylsiloxy group. These copolymers originally had a I : I composition between acrylate as an electron acceptor and the other two components as electron donors, and therefore could be recognized as copolymers of two alternating units, trimethylvinyland The conversion of lactonization was often beyond 86.5% (Flory's limit) being nearly 100%, especially in copolymers containing the phenyl acrylate component. Additional lactonization of the copolymers did not occur under the same conditions used in the work-up process. Hence, the realized conversion resulted from a statistical intramolecular reaction between trimethylsiloxy and alkoxycarbonyl groups. These terpolymers may thus be regarded as a model of the "specially-designed alternating copolymer" described in the preceding paper.KEY Recently, attention has been directed to the permeation and transport activities of particular ions of membranes of synthetic polymers containing lactone structures. 1 Such polymers can be synthesized either by polymerizing unsaturated lactone monomers or by reacting two neighboring substituents on a copolymer chain so as to form an ester bond. However, misaturated lactone monomers often show low polymerizabilities 2 and the substituents of a simple copolymer are not always arranged in favor of intramolecular lactonization. achieve 100% conversion. Inevitably, 13.5% of the substituents remain unreacted, as was experimentally observed in Hirooka's study. 4

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Mechanism of alternating copolymerization of acrylic monomers with donor monomers in the presence of lewis acid

Cited by 116 publications

References 85 publications

Alternierende Copolymerisation von Styrol und Benzylmethacrylat in Gegenwart von Ethylaluminiumsesquichlorid

Alternierende Copolymerisation von Styrol und Benzylmethacrylat in Gegenwart von Ethylaluminiumsesquichlorid

Intramolecular Reaction between Neighboring Substituents of Specially-Designed Alternating Copolymers

Ternary Copolymerization of Trimethylvinyloxysilane, Styrene, and Acrylic Esters Catalyzed by Organoaluminum Compounds

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