Copolymerization. X. The Effect of meta- and para-Substitution on the Reactivity of the Styrene Double Bond

Walling, Cheves; Briggs, Emorene R.; Wolfstirn, K. B.; Mayo, Frank R.

doi:10.1021/ja01184a072

Cited by 299 publications

(79 citation statements)

References 2 publications

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“…The free radical copolymerization (RP) of styrene with strong electron acceptors such as maleic anhydride (MAh), [18,[34][35][36][37] maleimide, [38] or N-substituted maleimides [19,39] was reported early in the polymer literature.…”

Section: The Basic Situation: Free Radical Copolymerization Of Styrenmentioning

confidence: 99%

Tailored Polymer Microstructures Prepared by Atom Transfer Radical Copolymerization of Styrene and N‐substituted Maleimides

Lutz¹,

Schmidt²,

Pfeifer³

2011

Macromol. Rapid Commun.

133

124

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In the present Feature Article, a kinetic strategy for controlling the microstructure of synthetic polymer chains prepared via a radical chain‐growth polymerization process is presented. This approach was recently developed in our laboratory and relies on the controlled kinetic addition of ultrareactive N‐substituted maleimides during the atom transfer radical polymerization of styrene. This method is experimentally straightforward and can be applied to a broad library of functional N‐substituted maleimides. Thus, this platform allows synthesis of unprecedented polymer materials such as 1D macromolecular arrays. The basic kinetic requirements, the experimental conditions, and the synthetic scope of this approach are discussed in details herein. magnified image

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Section: The Basic Situation: Free Radical Copolymerization Of Styrenmentioning

confidence: 99%

Tailored Polymer Microstructures Prepared by Atom Transfer Radical Copolymerization of Styrene and N‐substituted Maleimides

Lutz¹,

Schmidt²,

Pfeifer³

2011

Macromol. Rapid Commun.

133

124

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“…Equation (2-5) can be rearranged to: Except for the arrangements made in conneetion with the specific parameters arising from the experiments described in this thesis, equation (2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18) corresponds with integrated forms derived by other investigators (refs. 1, 11, 12, 13).…”

Section: Integration Of the Copolymerization Equationmentioning

confidence: 99%

“…Combination with k 11 • P 1 Q 1 exp(-e 1 2 ) , where the assumption is made that the "charge" on the double bond of a monoroer equals that on the end group of the radical of the same monoroer, leads to: -20) and (2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21) The product of reactivity ratios ~ • r 1 r 2 is an excellent measure of the alternation tendency in vinyl copolymeri- values of other monomars will repreaent the polarity on the double bond induced by a certain substituant. Q 0 only depends on r 2 = k 22 tk 21 and requires no adjustment owing to differences in double bond polarity.…”

Section: Pmentioning

confidence: 99%

Copolymerization of ethylene and vinyl acetate at low pressure: Determination of the kinetics by sequential sampling

German

Heikens

1971

J. Polym. Sci. A‐1 Polym. Chem.

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In behalf of a detailed study on the course of copolymerization reactions, this paper describes an improved and generally applicable experimental method and an efficient computational procedure to match. The experimental method is based on quantitative gas chromatography, and permits frequent measurement of the monomer feed composition throughout (co)polymerization processes at pressures up to 40 kgf/cm2 ( = 38.7 atm). The given method is applied to the study of the radical copolymerization of ethylene with vinyl acetate in a series of kinetic experiments, at 62°C and 35 kgf/cm2 ( = 33.9 atm) in tert‐butyl alcohol, in which 20–40% conversion is reached. Monomer feed composition and degree of conversion are entered into a computational procedure based on nonlinear least‐squares methods applied to the integrated version of the copolymer equation. The experimental data, covering a region of ethylene molar feed fractions between 0.24 and 0.74 and copolymer concentrations up to 8 wt‐%, are precisely consistent with the usual model. The respective reactivity ratios are r̂e = 0.743 ± 0.005 and r̂v = 1.515 ± 0.007.

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“…This work was later supported by Barb25. Complexes of a series of substituted styrenes and maleic anhydride 267 and their corresponding alternating copolymers were studied by Walling et al 26. These researchers concluded that the complex was determining the nature of the polymeric product of a free-radical initiation.…”

mentioning

confidence: 99%

The role of charge-transfer complexes in cyclocopolymerization

Butler¹

1970

Pure and Applied Chemistry

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ABSTRACT.Previous work from this laboratory has shown that certain 1 ,4-dienes which readily undergo cyclocopolymerization with certain alkenes also form chargetransfer complexes with the same alkenes. The results observed and the proposed cyciocopolymerization mechanism are consistent with participation of the charge-transfer complex as a distinct species in the copolymerization. This paper includes a discussion of an investigation to determine whether there was a dilution effect on the relative reactivities of the monomers in support of the charge-transfer participation concept, and whether the results of a suitable terpolymerization study would also support this postulate. In the system, divinyl ether-fumaronitrile, the maximum rate of copolymerization occurred at a monomer feed ratio of 1:2 and the composition of the copolymer was also 1:2 ata total monomer concentration of 3 moles/i. However, when the concentration was progressively lowered to 05 ml1, using the same monomer feed ratio, the fumaronitrile content of the copolymer decreased in a linear manner. In a series of terpolymerization experiments using the system, divinyl ethermaleic anhydride-acrylonitrile, it was shown that the divinyl ether-maleic anhydride ratio in the terpolymer was always greater than 1: 1 and had an upper limit of 1:2, regardless of the feed ratio of the termonomers. These results are consistent with the participation of the charge-transfer complex of divinyl ether and maleic anhydride in a copolymerization process with either maleic anhydride or acrylonitrile as the comonomer. Other systems which support these concepts are also presented. This paper emphasizes theoretical aspects of the problem rather than attempting to summarize the many examples of comonomer systems which have been found to participate in this interesting copolymerization.

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Copolymerization. X. The Effect of meta- and para-Substitution on the Reactivity of the Styrene Double Bond

Cited by 299 publications

References 2 publications

Tailored Polymer Microstructures Prepared by Atom Transfer Radical Copolymerization of Styrene and N‐substituted Maleimides

Tailored Polymer Microstructures Prepared by Atom Transfer Radical Copolymerization of Styrene and N‐substituted Maleimides

Copolymerization of ethylene and vinyl acetate at low pressure: Determination of the kinetics by sequential sampling

The role of charge-transfer complexes in cyclocopolymerization

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