Determination of relative rate constants of hydrolysis of poly[(dimethylamino)ethyl methacrylate]

Merle, Yves; Merle-Aubry, Liliane

doi:10.1021/ma00240a035

Cited by 3 publications

References 3 publications

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Determination of relative rate constants of reactions on polymers from the triad distribution data

Merle¹

1984

J. Polym. Sci. Polym. Phys. Ed.

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Since NMR spectroscopy has been available, allowing determination of the triad distribution in copolymer^,'-^ it has been possible to study the kinetics of reactions on polymers. The first attempt to evaluate relative rate constants was the curve fitting procedure of Klesper, Gronski, and Barth.4 The triad distribution of the different copolymers is calculated by simulation of the reaction on a computer, with selected rate constants. Then the results are compared with the experimental data.This method was improved by Klesper, Strasilla, and Barth? who found a procedure for calculating the relative rate constants graphically. Another graphical method was proposed by Harwood et al. using a triangular table.6Computer programs were devised by Bauer7 to calculate the triad distribution from the relative rate constants (SEQDIST), and the inverse problem (RATEFIND), with triad data of a single copolymer. But the relative rate constants are very uncertain as the result of amplification of experimental error in the triad data.s More accurate values can be obtained using triad data from a series of copolymers taken during the reaction. An improvemat of Klesper's graphical method5 is proposed here which allows the calculation of the relative rate constants by linear regression.We consider a chain of polymer composed of reactive groups A which after reaction become B units.

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Determination of relative rate constants of reactions on polymers from the triad distribution data

Merle¹

1984

J. Polym. Sci. Polym. Phys. Ed.

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Determination of the sequence distribution and ionization constant of poly(acrylic acid‐co‐vinylamine) by C‐13 NMR

Chang

Muccio

Pierre

1986

J. polym. sci., C Polym. symp.

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Three copolymers of poly(acrylic acid‐co‐vinylamine) containing 12% (SP12). 30% (SP30), and 52% (SP52) amino groups were synthesized from poly(acrylic acid) by means of the Schmidt reaction. These copolymers were analyzed by C‐13 NMR and the results compared wiih the previously analyzed homopolymers. The various comonomer sequence distributions were identified by means of peak areas. It was determined thai (1) the reactivity was not significantly influenced by the triad taciicity of the parent poly(acrylic acid), (2) the final copolymer is characterized by an essentially alternating sequence, and (3) there is extensive lactam formation between neighboring carboxyl and amino groups. In terms of nearest neighbor effects, the relative rales of amine formation are k1/k0 ≈ 0.3 and k2/k0 ≈ 0. A C‐13 NMR pH titration of SPI2 showed that the carboxyl group with a neighboring amino group is more acidic man a carboxyl group flanked by two carboxyl groups.

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Preparation of Ionic Polymers

Thomson

1986

Developments in Ionic Polymers—2

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Determination of relative rate constants of hydrolysis of poly[(dimethylamino)ethyl methacrylate]

Cited by 3 publications

References 3 publications

Determination of relative rate constants of reactions on polymers from the triad distribution data

Determination of relative rate constants of reactions on polymers from the triad distribution data

Determination of the sequence distribution and ionization constant of poly(acrylic acid‐co‐vinylamine) by C‐13 NMR

Preparation of Ionic Polymers

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