Solid State Cross-Linked Polypropylene via Reactive Extrusion: A Scalable Approach

High Resolution Image Download MS PowerPoint Slide Solid-state reactive extrusion provides a promising route for modifying semicrystalline polymers while minimizing degradation associated with conventional melt processing. Here, isotactic polypropylene was modified using benzoyl peroxide at 110 °C, below the polymer melting temperature. Under these conditions, radical reactions occur within the amorphous regions of the semicrystalline matrix while crystalline lamellae remain intact and restrict large-scale chain motion. FTIR and 13 C CP-MAS NMR analyses indicate that the polypropylene backbone is largely preserved after processing. Differential scanning calorimetry shows increased crystallization temperatures and reduced crystallinity, consistent with restricted chain mobility and network-induced nucleation. Rheological measurements reveal a progressive increase in the storage modulus with increasing peroxide concentration and a transition toward predominantly elastic behavior with the absence of G’/G” crossover, indicating increased molecular connectivity and network formation. Compared with conventional melt-state peroxide modification, the solid-state approach promotes intermolecular connectivity while limiting degradation pathways, providing an energy-efficient and scalable strategy for tailoring polypropylene properties.

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Publication Details

Journal
Macromolecules
Published
2026-07-02
DOI
https://doi.org/10.1021/acs.macromol.6c01058
Primary Topic
Polymer crystallization and properties
Type
article
Field-Weighted Citation Impact
0.00

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article

Solid State Cross-Linked Polypropylene via Reactive Extrusion: A Scalable Approach

Jonás José Perez Bravo, Javier González‐Benito, Jules A.W. Harings
Macromolecules
Polymer crystallization and properties
article

Solid State Cross-Linked Polypropylene via Reactive Extrusion: A Scalable Approach

Jonás José Perez Bravo, Javier González‐Benito, Jules A.W. Harings
article en

Abstract

High Resolution Image Download MS PowerPoint Slide Solid-state reactive extrusion provides a promising route for modifying semicrystalline polymers while minimizing degradation associated with conventional melt processing. Here, isotactic polypropylene was modified using benzoyl peroxide at 110 °C, below the polymer melting temperature. Under these conditions, radical reactions occur within the amorphous regions of the semicrystalline matrix while crystalline lamellae remain intact and restrict large-scale chain motion. FTIR and 13 C CP-MAS NMR analyses indicate that the polypropylene backbone is largely preserved after processing. Differential scanning calorimetry shows increased crystallization temperatures and reduced crystallinity, consistent with restricted chain mobility and network-induced nucleation. Rheological measurements reveal a progressive increase in the storage modulus with increasing peroxide concentration and a transition toward predominantly elastic behavior with the absence of G’/G” crossover, indicating increased molecular connectivity and network formation. Compared with conventional melt-state peroxide modification, the solid-state approach promotes intermolecular connectivity while limiting degradation pathways, providing an energy-efficient and scalable strategy for tailoring polypropylene properties.

Macromolecules
Maastricht University (NL), Ministerio de Ciencia y Tecnología (AR), Instituto Tecnológico de la Energía (ES), Universidad Carlos III de Madrid (ES)
European Commission, Universidad Carlos III de Madrid, HORIZON EUROPE Framework Programme, HORIZON EUROPE Marie Sklodowska-Curie Actions
Openalex Percentile: Top 15%
Polymer crystallization and properties
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