Transfer to Polymer and Long‐Chain Branching in PLP–SEC of Acrylates

Castignolles, Patrice

doi:10.1002/marc.200900530

Cited by 32 publications

(50 citation statements)

References 54 publications

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“…LCB was detected in P2EHA produced by pulsed laser polymerization (PLP) using multiple‐detection size‐exclusion chromatography (SEC), even at low temperature (down to −34 °C) and at low conversion . The local dispersities, Ð ( V h ), obtained can reach values close to 2.…”

Section: Introductionmentioning

confidence: 99%

“…The local dispersities, Ð ( V h ), obtained can reach values close to 2. This means that the error in molar mass determination using SEC can reach 100% . The occurrence of LCB, leading to inaccurate molar mass determination by SEC, is more important for P2EHA than for acrylates with shorter side groups, like P n BA and poly(methyl acrylate).…”

Section: Introductionmentioning

confidence: 99%

“…Even though there have been several attempts to determine k p in 2EHA polymerization, it is suspected that the obtained values suffer from relatively low accuracy due to LCB. For example, the error in PLP‐SEC values for P2EHA was estimated to be between 30–100% for −34 °C < θ < 22 °C …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Effects of Chain Transfer Agent and Temperature on Branching and β‐Scission in Radical Polymerization of 2‐Ethylhexyl Acrylate

Lena

Deschamps

Sciortino

et al. 2018

Macro Chemistry & Physics

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Poly(2‐ethylhexyl acrylate) is synthesized by conventional radical bulk polymerization both with and without 1‐dodecane thiol as chain transfer agent (CTA) at temperatures from 4 to 140 °C. Electrospray‐ionization mass spectrometry is used to analyze the polymer. This reveals the occurrence of significant β‐scission at high temperature and confirms the presence of CTA‐capped polymers at all temperatures, as well as combination products from 4 to 65 °C. Subsequent 13C melt‐state NMR analysis allows quantification of branching and β‐scission. Both are reduced when CTA is present, consistent with a “patching” effect. As expected, the amounts of β‐scission and branching increase with synthesis temperature, although β‐scission dominates at the highest temperature. The backbiting rate coefficient of 2‐ethylhexyl acrylate is determined from NMR results, taking β‐scission into account for the first time. Remarkable agreement with literature kbb values is obtained, especially for activation energy. This strongly suggests family‐type behavior for acrylate kbb.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Effects of Chain Transfer Agent and Temperature on Branching and β‐Scission in Radical Polymerization of 2‐Ethylhexyl Acrylate

Lena

Deschamps

Sciortino

et al. 2018

Macro Chemistry & Physics

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“…Light scattering yields M w (V h ). When the local dispersity, M w (V h )/M n (V h ), is significantly greater than one, then the accuracy of the determined molecular weight distribution is limited [31]. The hydrodynamic volume distributions can be used instead.…”

Section: Is the Weight Distribution Of Molecular Weights M And Hydrodmentioning

confidence: 98%

Viscosimetric detection in size‐exclusion chromatography (SEC/GPC): The Goldwasser method and beyond

Castignolles

Gaborieau

2010

J of Separation Science

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Size-exclusion chromatography (SEC or GPC) is the most widely used separation method to characterize polymers. The high level of complexity of most polymeric materials necessitates the use of not only concentration-sensitive detection but also structure-sensitive detection. Viscometry is usually used in conjunction with a concentration-sensitive detector and universal calibration to determine molecular weights of polymers. Goldwasser proposed to use a viscometer as a single detector to determine number-average molecular weights, M(n) (ACS Symposium Series, 521, 143). The method is particularly of interest when concentration-sensitive detection is not available, because the sample is isorefractive or not UV-absorbing, or because composition is not constant (copolymers). It has known very little applications so far. It actually does not only allow determining M(n), but also the number hydrodynamic volume distribution. This opens a wider range of applications for the Goldwasser method. Size-exclusion chromatography only yields inaccurate molecular weight distributions for some complex branched polymers. Hydrodynamic volume distributions have then a strong potential for comparative studies owing to their far higher accuracy. Our experimental tests highlight the fact that the method is highly sensitive to noise and careful optimization of the injection concentration is needed, but number distribution can be obtained as well as M(n).

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“…in the case of branched polymers. [13,20,21] Due to these different factors, SEC suffers generally from poor reproducibility, especially for aqueous SEC. [22][23][24] In the case of poly(acrylic acid), there is an additional controversy arising from significantly different molecular weights determined by aqueous SEC and organic SEC.…”

Section: Introductionmentioning

confidence: 99%

Molecular Weight and Tacticity of Oligoacrylates by Capillary Electrophoresis - Mass Spectrometry

et al. 2010

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Oligo(acrylic acid) efficiently stabilizes polymeric particles, especially particles produced by reversible additionfragmentation chain transfer (RAFT) (as hydrophilic block of an amphiphilic copolymer). Capillary electrophoresis (CE) has a far higher resolution power to separate these oligomers than the commonly used size exclusion chromatography. Coupling CE to electrospray ionization mass spectrometric detection unravels the separation mechanism. CE separates these oligomers, not only according to their degree of polymerization, but also according to their tacticity, in agreement with NMR analysis. Such analysis will provide insight into the role of these oligomers as stabilizers in emulsion polymerization, and into the mechanism of the RAFT polymerization with respect to degree of polymerization and tacticity.

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Transfer to Polymer and Long‐Chain Branching in PLP–SEC of Acrylates

Cited by 32 publications

References 54 publications

Effects of Chain Transfer Agent and Temperature on Branching and β‐Scission in Radical Polymerization of 2‐Ethylhexyl Acrylate

Effects of Chain Transfer Agent and Temperature on Branching and β‐Scission in Radical Polymerization of 2‐Ethylhexyl Acrylate

Viscosimetric detection in size‐exclusion chromatography (SEC/GPC): The Goldwasser method and beyond

Molecular Weight and Tacticity of Oligoacrylates by Capillary Electrophoresis - Mass Spectrometry

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