Characterization of the Chemical Composition Distribution of Poly(<i>n</i>‐butyl acrylate‐stat‐acrylic acid)s

Maier, Helena; Malz, Frank; Radke, Wolfgang

doi:10.1002/macp.201400399

Cited by 8 publications

(4 citation statements)

References 19 publications

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“…To monitor and improve the industrial processes as well as improving end-product properties, there is a need for characterization of the acid incorporation in polymers, as is it responsible for the stabilization of the polymer particles. Analysis of the average-acid content in copolymers can be performed with titration [1] , nuclear-magnetic-resonance (NMR) spectroscopy, liquidchromatographic (LC) separation techniques in either reversedor normal-phase modes [2][3][4][5][6][7] and gradient-size-exclusion chromatography (gradient-SEC) [8][9][10][11] . Although the described separation methodologies have a broad application window, specifically for copolymers, the currently available separation methodologies yield no direct correlation between retention behaviour and presence or distribution of acid groups for samples with compositional differences, because retention also depends on the overall polymer polarity.…”

Section: Introductionmentioning

confidence: 99%

Charge-based separation of synthetic macromolecules by non-aqueous ion exchange chromatography

Brooijmans

Breuer

Schoenmakers

et al. 2020

Journal of Chromatography A

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Section: Introductionmentioning

confidence: 99%

Charge-based separation of synthetic macromolecules by non-aqueous ion exchange chromatography

Brooijmans

Breuer

Schoenmakers

et al. 2020

Journal of Chromatography A

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“…It was further shown that a relation between sequence length heterogeneity and the molar mass distribution could be achieved; however, a number of conditions were required, including the intrachain interaction of the different monomers to be different to the monomers of the same type, appropriate solvation conditions for the chemical functionalities, and the architecture of the copolymer should remain the same as a function of the molar mass . SEC gradient was shown to be able to determine the chemical composition distribution of statistical copolymers . The coupling of SEC and gradient elution liquid chromatography , was shown to be required for the analysis of both synthetic and artificial copolymers since both dimensions suffered from coelution when performed individually.…”

mentioning

confidence: 99%

“…6 SEC gradient was shown to be able to determine the chemical composition distribution of statistical copolymers. 7 The coupling of SEC and gradient elution liquid chromatography 8,9 was shown to be required for the analysis of both synthetic and artificial copolymers since both dimensions suffered from coelution when performed individually. The dispersity of the distribution of compositions is not determined in the literature.…”

mentioning

confidence: 99%

Quantifying the Heterogeneity of Chemical Structures in Complex Charged Polymers through the Dispersity of Their Distributions of Electrophoretic Mobilities or of Compositions

Thevarajah¹,

Sutton²,

Maniego³

et al. 2016

Anal. Chem.

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The complexity of synthetic and natural polymers used in industrial and medical applications is expanding; thus, it becomes increasingly important to improve and develop methods for their molecular characterization. Free-solution capillary electrophoresis is a robust technique for the separation and characterization of both natural and synthetic complex charged polymers. In the case of polyelectrolytes, free-solution capillary electrophoresis is in the "critical conditions" (CE-CC): it allows their separation by factors other than molar mass for molar masses typically higher than 20000 g/mol. This method is thus complementary to size-exclusion chromatography (SEC). SEC is widely used to determine molar mass distributions and their dispersities. Utilizing CE-CC, an analogous calculation of dispersity based on the distributions of electrophoretic mobilities was derived and the heterogeneity of composition or branching in different polysaccharides or synthetic polymers was obtained in a number of experimental cases. Calculations are based on a ratio of moments and could therefore be compared to simulations of polymerization processes, in analogy to the work performed on molar mass distributions. Among four possible types of dispersity, the most precise values were obtained with the calculation analogous with the dispersity of molar mass distribution Mw/Mn. In addition, the dispersity value allows conclusions based on a single value: the closer the dispersity is to 1, the more homogeneous the polymer is in terms of composition or branching. This approach allows the analysis of dispersity of important molecular attributes of polymers other than molar mass and aims at improving the overall molecular characterization of both synthetic and natural polymers. The dispersity can also be monitored online while performing a chemical reaction within the CE instrument.

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“…Therefore, a triad distribution study will not be possible to establish the formation of gradient structures in the AOST-tBA or HOST-tBA copolymer systems. Though few recent studies reported that it is possible to determine the distribution of chemical composition which involves complex methods [367][368][369].…”

Section: Introductionmentioning

confidence: 99%

Understanding and controlling the structure of thin polymer films used in photolithography

Alam¹

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Line edge roughness (LER) is one of the major impediments to the semiconductor industry achieving the desired device performance and satisfying the goals set by International Technology Roadmap for Semiconductor (ITRS). LER is defined as any sort of unwanted roughness in semiconductor features, and among many other factors, structural heterogeneity of the photoresist materials is one of the sources of LER in photolithographic devices. This gives the motivation to study a new class of copolymer named 'gradient copolymer', which is unique in terms of the copolymer chain structure. The copolymer composition of gradient copolymers changes from one end of the chain to the other gradually, while the copolymer composition is on average constant along the chains for conventional statistical copolymers. In contrast, block copolymers show an abrupt switch in the polymer composition. In this study, statistical, block and gradient copolymers have been synthesized for two different monomer pairs (styreneacrylonitrile and hydroxystyrene t-butyl acrylate) using reversible addition-fragmentation chain transfer (RAFT) and conventional radical polymerization (CvRP) method, and their surface properties extensively studied.The kinetics of copolymerization of styrene (St) and acrylonitrile (AN) by RAFT method was studied in detail. Reactivity ratios of St and AN were determined for nine different feed compositions for RAFT, and the effect of solvent on reactivity ratios was discussed based on the bootstrap model. Batch polymerization of styrene (St) and acrylonitrile (AN) yielded statistical and spontaneous gradient copolymers depending on the monomer feed ratio, and the chain structures were confirmed from the change in the copolymer composition. St-and AN-centered triad distributions were determined using quantitative 13 C NMR. Using the continuous feeding approach, forced gradient St-AN copolymers were prepared, and St-block-AN copolymers synthesized by the chain extension method. Statistical, gradient and block copolymers have also been synthesized for the acetoxystyrenet-butyl acrylate monomer system. The statistical and gradient structures were confirmed from the change in the composition since this pair does not provide any well resolved peaks for different triad sequences in 13 C NMR. Hydroxystyrenet-butyl acrylate (HOST-tBA) copolymers were prepared by selective hydrolysis of 4-acetoxystyrenet-butyl acrylate (AOST-tBA) copolymers.The properties of the both copolymer systems were found to be strongly dependent on the copolymer structure. A unique broad glass transition was observed for the gradient copolymers, which is different from behaviour of the statistical and block copolymers. Surface properties of St-AN statistical, gradient and block copolymer thin films were found to be very different due to the

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Characterization of the Chemical Composition Distribution of Poly(n‐butyl acrylate‐stat‐acrylic acid)s

Cited by 8 publications

References 19 publications

Charge-based separation of synthetic macromolecules by non-aqueous ion exchange chromatography

Charge-based separation of synthetic macromolecules by non-aqueous ion exchange chromatography

Quantifying the Heterogeneity of Chemical Structures in Complex Charged Polymers through the Dispersity of Their Distributions of Electrophoretic Mobilities or of Compositions

Understanding and controlling the structure of thin polymer films used in photolithography

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