Michael addition in reactive extrusion: A facile sustainable route to developing phosphorus based flame retardant materials

Simonetti, Pietro; Nazir, Rashid; Gooneie, Ali; Lehner, Sandro; Jovic, Milijana; Salmeia, Khalifah A.; Hufenus, Rudolf; Rippl, Alexandra; Kaiser, Jean‐Pierre; Hirsch, Cordula; Rubi, Bertran; Gaan, Sabyasachi

doi:10.1016/j.compositesb.2019.107470

Cited by 26 publications

(12 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This can be attributed to possible cyclization reactions that impede polymerization . The low-temperature gelation under cross-linker/catalyst-free condition and amine specific reactivity is a quite unique feature, enabling formulations to incorporate thermosensitive molecules or reagents. , …”

Section: Results and Discussionmentioning

confidence: 99%

“…55 The low-temperature gelation under cross- linker/catalyst-free condition and amine specific reactivity is a quite unique feature, enabling formulations to incorporate thermosensitive molecules or reagents. 30,56 Alkyl chain lengths between piperidine and piperazine units of diamines were found to alter the hydrophilicity of the gels (Figure S17). The use of piperazine led to the formation of a hydrogel differing in comparison to the hydrophobic gels obtained for amines with longer alkyl bridge (Gel-B to Gel-E).…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Structurally Tunable pH-responsive Phosphine Oxide Based Gels by Facile Synthesis Strategy

Nazir

Parida

Guex

et al. 2020

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

Design and synthesis of nanostructured responsive gels have attracted increasing attention, particularly in the biomedical domain. Polymer chain configurations and nanodomain sizes within the network can be used to steer their functions as drug carriers. Here, a catalyst-free facile one-step synthesis strategy is reported for the design of pH-responsive gels and controlled structures in nanoscale. Transparent and impurity free gels were directly synthesized from trivinylphosphine oxide (TVPO) and cyclic secondary diamine monomers via Michael addition polymerization under mild conditions. NMR analysis confirmed the consumption of all TVPO and the absence of side products, thereby eliminating post purification steps. The small-angle X-ray scattering (SAXS) elucidates the nanoscale structural features in gels, that is, it demonstrates the presence of collapsed nanodomains within gel networks and it was possible to tune the size of these domains by varying the amine monomers and the nature of the solvent. The fabricated gels demonstrate structure tunability via solvent–polymer interactions and pH specific drug release behavior. Three different anionic dyes (acid blue 80, acid blue 90, and fluorescein) of varying size and chemistry were incorporated into the hydrogel as model drugs and their release behavior was studied. Compared to acidic pH, a higher and faster release of acid blue 80 and fluorescein was observed at pH 10, possibly because of their increased solubility in alkaline pH. In addition, their release in phosphate buffered saline (PBS) and simulated body fluid (SBF) matrix was positively influenced by the ionic interaction with positively charged metal ions. In the case of hydrogel containing acid blue 90 a very low drug release (<1%) was observed, which is due to the reaction of its accessible free amino group with the vinyl groups of the TVPO. In vitro evaluation of the prepared hydrogel using human dermal fibroblasts indicates no cytotoxic effects, warranting further research for biomedical applications. Our strategy of such gel synthesis lays the basis for the design of other gel-based functional materials.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Structurally Tunable pH-responsive Phosphine Oxide Based Gels by Facile Synthesis Strategy

Nazir

Parida

Guex

et al. 2020

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

show abstract

“…REX can also be used for the preparation of phosphorylated-macromolecules in the presence of another polymer. Simonetti et al [84] prepared phosphorylated-polyamide 6 (PA6) via a Michael-addition reaction of divinylphenylphosphine oxide and piperazine by REX. The materials obtained, physical blends of PA and phosphine oxide macromolecules, presented non-leaching behavior and superior LOI values than virgin PA.…”

Section: Integration Of Flame Retardants Into Polymersmentioning

confidence: 99%

Flame retardant polymer materials: An update and the future for 3D printing developments

Vahabi

Laoutid

Mehrpouya

et al. 2021

Materials Science and Engineering: R: Reports

167

View full text Add to dashboard Cite

“…However, structural changes introduced in the chemical structure of the PA6 back chain produce new challenges regarding the chemical recyclability. The second proposed direction for solving the flammability problem of the PA6 film and textile materials is based on the in situ synthesis of phosphine-oxide-based macromolecules during the PA6 reactive extrusion process [26]. In this case, formation of phosphine-oxide-based oligomeric and low-molecular-weight polymers was found to be beneficial for improved flame retardancy and non-leaching behavior.…”

Section: Introductionmentioning

confidence: 99%

Effect of Different Flame-Retardant Bridged DOPO Derivatives on Properties of in Situ Produced Fiber-Forming Polyamide 6

et al. 2020

View full text Add to dashboard Cite

The production of sustainable and effective flame retardant (FR) polyamide 6 (PA6) fibrous materials requires the establishment of a novel approach for the production of polyamide 6/FR nanodispersed systems. This research work explores the influence of three different flame-retardant bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives on the comprehensive properties of in situ produced PA6/FR systems. To this end, in situ water-catalyzed ring-opening polymerization of ε-caprolactam was conducted in the presence of three different bridged DOPO derivatives, e.g., one P−N bond phosphonamidate derivative and two P−C bond phosphinate derivatives. The selected bridged DOPO derivatives mainly act in the gas phase at the temperatures that relatively match the PA6 pyrolysis specifics. The effects of the FRs on the dispersion state, morphological, molecular, structural, melt-rheological, and thermal properties of the in situ synthesized PA6 were evaluated. The specific advantage of this approach is one-step production of PA6 with uniformly distributed nanodispersed FR, which was obtained in the case of all three applied FRs. However, the applied FRs differently interacted with monomer and polymer during the polymerization, which was reflected in the length of PA6 chains, crystalline structure, and melt-rheological properties. The applied FRs provided a comparable effect on the thermal stability of PA6 and stabilization of the PA6/FR systems above 450 °C in the oxygen-assisted pyrolysis. However, only with the specifically designed FR molecule were the comprehensive properties of the fiber-forming PA6 satisfied for the continuous conduction of the melt-spinning process.

show abstract

Michael addition in reactive extrusion: A facile sustainable route to developing phosphorus based flame retardant materials

Cited by 26 publications

References 49 publications

Structurally Tunable pH-responsive Phosphine Oxide Based Gels by Facile Synthesis Strategy

Structurally Tunable pH-responsive Phosphine Oxide Based Gels by Facile Synthesis Strategy

Flame retardant polymer materials: An update and the future for 3D printing developments

Effect of Different Flame-Retardant Bridged DOPO Derivatives on Properties of in Situ Produced Fiber-Forming Polyamide 6

Contact Info

Product

Resources

About