“To Be or Not to Be” of a Polymer Nanogel—Unravelling the Relationship of Product Properties vs. Synthesis Conditions Governing the Radiation Crosslinking of Poly(acrylic acid) Using GPC/SEC—MALLS

In this paper, a state-of-the-art multi-detection gel permeation chromatography/size exclusion chromatography (GPC/SEC) system including multi-angle laser light scattering (MALLS) is applied to monitor radiation-induced synthesis of internally crosslinked nanostructures from poly(acrylic acid) (PAA)...

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Main Authors: Sławomir Kadłubowski, Beata Paulina Rurarz, Joanna Raczkowska, Carlo Dessy, Piotr Ulański
Format: Article
Language:English
Published: MDPI AG 2023-11-01
Series:Materials
Subjects:
Online Access:https://www.mdpi.com/1996-1944/16/23/7467
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author Sławomir Kadłubowski
Beata Paulina Rurarz
Joanna Raczkowska
Carlo Dessy
Piotr Ulański
author_facet Sławomir Kadłubowski
Beata Paulina Rurarz
Joanna Raczkowska
Carlo Dessy
Piotr Ulański
author_sort Sławomir Kadłubowski
collection DOAJ
description In this paper, a state-of-the-art multi-detection gel permeation chromatography/size exclusion chromatography (GPC/SEC) system including multi-angle laser light scattering (MALLS) is applied to monitor radiation-induced synthesis of internally crosslinked nanostructures from poly(acrylic acid) (PAA). The aim is to demonstrate that this modern tool yields a more detailed picture of reaction mechanism and product structure than the techniques used to date. The prevailing intramolecular crosslinking narrows the molecular weight distribution from M<sub>w</sub>/M<sub>n</sub> = 3.0 to 1.6 for internally crosslinked structures. A clear trend from over 0.7 to 0.5 in the Mark–Houwink exponent and a decrease in R<sub>g</sub>/R<sub>h</sub> from 1.7 to 1.0 point to the formation of nanogels, more rigid and less permeable than the starting coils. Changes in the coil contraction factor (<i>g</i>′ = [<i>η</i>]<i><sub>irradiated</sub></i>/[<i>η</i>]<i><sub>linear</sub></i>) as a function of the radical density revealed the existence of two modes in intramolecular crosslinking, the initial one (up to 0.075 radicals per monomer unit) where the compactness of products changes strongly with progressing crosslinking and a second one where further compacting is suppressed by the lower flexibility of the partially crosslinked chain segments. This indicates a transition from soft, still internally crosslinkable nanogels to more rigid structures, less prone to further intramolecular loop formation. Our findings provide means for the tailored design of new PAA nanomaterials.
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spelling doaj.art-65608e4d6d6c41a796afde75748144a02023-12-08T15:21:20ZengMDPI AGMaterials1996-19442023-11-011623746710.3390/ma16237467“To Be or Not to Be” of a Polymer Nanogel—Unravelling the Relationship of Product Properties vs. Synthesis Conditions Governing the Radiation Crosslinking of Poly(acrylic acid) Using GPC/SEC—MALLSSławomir Kadłubowski0Beata Paulina Rurarz1Joanna Raczkowska2Carlo Dessy3Piotr Ulański4Institute of Applied Radiation Chemistry, Faculty of Chemistry, Lodz University of Technology, Wroblewskiego 15, 93-590 Lodz, PolandInstitute of Applied Radiation Chemistry, Faculty of Chemistry, Lodz University of Technology, Wroblewskiego 15, 93-590 Lodz, PolandInstitute of Applied Radiation Chemistry, Faculty of Chemistry, Lodz University of Technology, Wroblewskiego 15, 93-590 Lodz, PolandTesta Analytical Solutions e.K., Sophienstr. 5, 12203 Berlin, GermanyInstitute of Applied Radiation Chemistry, Faculty of Chemistry, Lodz University of Technology, Wroblewskiego 15, 93-590 Lodz, PolandIn this paper, a state-of-the-art multi-detection gel permeation chromatography/size exclusion chromatography (GPC/SEC) system including multi-angle laser light scattering (MALLS) is applied to monitor radiation-induced synthesis of internally crosslinked nanostructures from poly(acrylic acid) (PAA). The aim is to demonstrate that this modern tool yields a more detailed picture of reaction mechanism and product structure than the techniques used to date. The prevailing intramolecular crosslinking narrows the molecular weight distribution from M<sub>w</sub>/M<sub>n</sub> = 3.0 to 1.6 for internally crosslinked structures. A clear trend from over 0.7 to 0.5 in the Mark–Houwink exponent and a decrease in R<sub>g</sub>/R<sub>h</sub> from 1.7 to 1.0 point to the formation of nanogels, more rigid and less permeable than the starting coils. Changes in the coil contraction factor (<i>g</i>′ = [<i>η</i>]<i><sub>irradiated</sub></i>/[<i>η</i>]<i><sub>linear</sub></i>) as a function of the radical density revealed the existence of two modes in intramolecular crosslinking, the initial one (up to 0.075 radicals per monomer unit) where the compactness of products changes strongly with progressing crosslinking and a second one where further compacting is suppressed by the lower flexibility of the partially crosslinked chain segments. This indicates a transition from soft, still internally crosslinkable nanogels to more rigid structures, less prone to further intramolecular loop formation. Our findings provide means for the tailored design of new PAA nanomaterials.https://www.mdpi.com/1996-1944/16/23/7467nanogelspoly(acrylic acid)radiation synthesisgel permeation chromatographymulti-angle laser light scattering
spellingShingle Sławomir Kadłubowski
Beata Paulina Rurarz
Joanna Raczkowska
Carlo Dessy
Piotr Ulański
“To Be or Not to Be” of a Polymer Nanogel—Unravelling the Relationship of Product Properties vs. Synthesis Conditions Governing the Radiation Crosslinking of Poly(acrylic acid) Using GPC/SEC—MALLS
Materials
nanogels
poly(acrylic acid)
radiation synthesis
gel permeation chromatography
multi-angle laser light scattering
title “To Be or Not to Be” of a Polymer Nanogel—Unravelling the Relationship of Product Properties vs. Synthesis Conditions Governing the Radiation Crosslinking of Poly(acrylic acid) Using GPC/SEC—MALLS
title_full “To Be or Not to Be” of a Polymer Nanogel—Unravelling the Relationship of Product Properties vs. Synthesis Conditions Governing the Radiation Crosslinking of Poly(acrylic acid) Using GPC/SEC—MALLS
title_fullStr “To Be or Not to Be” of a Polymer Nanogel—Unravelling the Relationship of Product Properties vs. Synthesis Conditions Governing the Radiation Crosslinking of Poly(acrylic acid) Using GPC/SEC—MALLS
title_full_unstemmed “To Be or Not to Be” of a Polymer Nanogel—Unravelling the Relationship of Product Properties vs. Synthesis Conditions Governing the Radiation Crosslinking of Poly(acrylic acid) Using GPC/SEC—MALLS
title_short “To Be or Not to Be” of a Polymer Nanogel—Unravelling the Relationship of Product Properties vs. Synthesis Conditions Governing the Radiation Crosslinking of Poly(acrylic acid) Using GPC/SEC—MALLS
title_sort to be or not to be of a polymer nanogel unravelling the relationship of product properties vs synthesis conditions governing the radiation crosslinking of poly acrylic acid using gpc sec malls
topic nanogels
poly(acrylic acid)
radiation synthesis
gel permeation chromatography
multi-angle laser light scattering
url https://www.mdpi.com/1996-1944/16/23/7467
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