Predicting and Measuring the Sequence Distribution of Addition Polymers

Montaudo, Maurizio S.

doi:10.1007/978-1-4419-6800-5_10

Cited by 2 publications

(3 citation statements)

References 82 publications

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“…Finally, our analysis predicts an outright shift in the low molecular weight region of the spectrum to the spacing of the unit with the narrower distribution along with a shift to asymmetric, "sawtooth" shaped peak clusters, both due to the tail of the MWD. We believe our investigation is significant because, despite the observation of some of these particular features both experimentally [5][6][7][8][9][10][11][12][13][14][15]17,[20][21][22]27 and numerically, 24−26 until now, no explanation has been provided for their origins. Furthermore, the results of this analysis can be applied broadly to copolymers and provide simple expressions to examine mass spectra of copolymers of any identity, composition, length, distribution, or architecture.…”

Section: Introductionmentioning

confidence: 97%

“…The most prominent feature in the mass spectrum of a copolymer is that the peaks corresponding to individual copolymer chains are grouped into clusters. − ,,− , For simplicity, the following discussion describes a two-component copolymer; however, the ideas and definitions extend to copolymers of more than two components, as will be demonstrated later. Therefore, in a copolymer of A and B units, each cluster consists of copolymer chains all with the same degree of polymerization but with different compositions of A and B.…”

Section: Introductionmentioning

confidence: 99%

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On the Origin of the Major Peak Cluster Spacing in the Mass Spectra of Copolymers

2013

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Mass spectrometry (MS) is a uniquely informative technique in the characterization of copolymers, where spectra prominently feature peak clustering. The spacing of these clusters, in general, is dominated by the spacing of one repeat unit, and contained herein is the theory to explain this observation. Extension of this theory also explains the more subtle observation that, even though the spacing is generally that of one unit, occasionally, the spacing between the maxima of adjacent clusters shifts by that of the other unit. Furthermore, the theory predicts that, in the low molecular weight region of the spectrum, there is a total switch to the spacing of the other unit along with asymmetric peak clusters that have a “sawtooth” shape. The analysis uses the Gaussian, log–normal, and Schulz–Zimm models as well as the random coupling hypothesis to explicitly demonstrate that (1) the major peak cluster spacing naturally arises from the unit in the copolymer with the widest distribution, as measured by the scaled standard deviation, (2) the spacing shift naturally occurs due to the marginal probabilities away from the spectrum maximum, and (3) the low molecular weight switch is a natural consequence of the tail of the distribution of the unit with the widest distribution. Results are provided to predict which unit in the copolymer will govern the major peak cluster spacing, how often the spacing will shift to that of another unit in the middle and high molecular weight regions of the spectrum, the molecular weight and composition of the maximum peak in every cluster, and the molecular weight below which the spacing will be that of the another unit. We believe that our results are the first to provide tangible theory to explain the previously unknown origins of these empirically observed phenomena.

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Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

On the Origin of the Major Peak Cluster Spacing in the Mass Spectra of Copolymers

2013

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“…One of the chief challenges in unraveling the relationship between sequence and properties is that experimental techniques allow some measurements of sequence to be uncovered, but do not yet measure explicit sequence distributions. One of the most useful methods to measure sequence information is nuclear magnetic resonance (NMR) spectroscopy, which can be used to measure fragments such as dyads and triads. In addition, the chemical composition distribution (CCD), which can be the fingerprint of the sequence, can be measured using MALDI‐ToF‐MS .…”

Section: Introductionmentioning

confidence: 99%

Design of Copolymers Based on Sequence Distribution for a Targeted Molecular Weight and Conversion

Regatte

Gao

Konstantinov

et al. 2014

Macromol. Theory Simul.

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It is challenging to track explicit copolymer sequences and related measures using continuum kinetic models. We developed a generalized framework based on kinetic Monte Carlo (KMC) to model free radical polymerization of any number of monomers to obtain the explicit sequence and its distribution. The KMC framework was applied to copolymerization of butyl acrylate/methyl methacrylate (BA/MMA) and methyl acrylate/methyl methacrylate (MA/MMA), and the simulation output was compared with experimental results. Sequence characteristics that were not accessible via experiments were then predicted. Explicit monomer sequence information was used to construct operating diagrams to design a representative copolymer recipe with a specific sequence target as a function of molecular weight and monomer conversion.

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Predicting and Measuring the Sequence Distribution of Addition Polymers

Cited by 2 publications

References 82 publications

On the Origin of the Major Peak Cluster Spacing in the Mass Spectra of Copolymers

On the Origin of the Major Peak Cluster Spacing in the Mass Spectra of Copolymers

Design of Copolymers Based on Sequence Distribution for a Targeted Molecular Weight and Conversion

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