Synthesis of microsphere-loaded porous polymers by combining emulsion and dispersion polymerisations in supercritical carbon dioxide

Boyère, Cédric; Léonard, A.; Grignard, Bruno; Favrelle, Audrey; Pirard, Jean‐Paul; Paquot, Michel; Jérôme, Christine; Debuigne, Antoine

doi:10.1039/c2cc33978a

Cited by 16 publications

(17 citation statements)

References 31 publications

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“…The voids were 10–80 µm in size, and the interconnected pores were approximately 0.5–25 µm; and a hierarchical porous structure was formed . The density of all the as‐synthesized MOF/PAMs was less than 0.2 g cm −3 (see Table ), which was slightly lighter than that of the other PAM monoliths (density > 0.2 g cm −3 ) reported in literature . This finding was ascribed to the larger void sizes in Pickering emulsion‐templated porous materials than in surfactant‐emulsified conventional emulsions .…”

Section: Resultsmentioning

confidence: 76%

“…[29] The density of all the as-synthesized MOF/PAMs was less than 0.2 g cm −3 (see Table 1), which was slightly lighter than that of the other PAM monoliths (density > 0.2 g cm −3 ) reported in literature. [37,52] This finding was ascribed to the larger void sizes in Pickering emulsion-templated porous materials than in surfactant-emulsified conventional emulsions. [53] However, HIPE became unstable when the content of HKUST-1 increased to 20 wt% (even 30 wt%, based on H 2 O), and the as-synthesized MOF/PAMs only accounted for 50 vol% of the entire reactor, indicating that only partial CO 2 have formed the C/W emulsion.…”

Section: Mof/pams With Different Hkust-1 Contentsmentioning

confidence: 99%

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High‐Performance Composite Monolith Synthesized via HKUST‐1 Stabilized HIPEs and Its Adsorptive Properties

Yang

Cao

et al. 2018

Macro Materials & Eng

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This paper presents a green and facile method for generating a composite monolith. HKUST‐1 (Pickering emulsifier) and PVA (co‐emulsifier), are used to stabilize supercritical carbon dioxide in water as high internal phase emulsion template to prepare interconnected hydrophilic porous monoliths. The effects of HKUST‐1 contents and CO2 densities on the performance of MOF/ polyacrylamide (PAM) polyHIPEs are investigated. The as‐synthesized MOF/PAM composites are characterized by FT‐IR, SEM, XRD, and TGA. The SEM patterns show that the composites are interconnected, the void sizes are 10–80 µm, and the interconnected pore throats are approximately 0.5–25 µm. The rheological and DMA measurement results indicate that the viscoelasticity and mechanical properties of the composites greatly improve after HKUST‐1 is embedded. Furthermore, the adsorptive properties of MOF/PAM to bovine serum albumin (BSA) are studied, and the adsorption capacity of MOF/PAM enhances with the increase in HKUST‐1 content. The adsorption capacity of the composite with 7 wt% HKUST‐1 reached 350.4 mg g−1 in 1.0 g L−1 BSA solution.

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Section: Resultsmentioning

confidence: 76%

Section: Mof/pams With Different Hkust-1 Contentsmentioning

confidence: 99%

High‐Performance Composite Monolith Synthesized via HKUST‐1 Stabilized HIPEs and Its Adsorptive Properties

Yang

Cao

et al. 2018

Macro Materials & Eng

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“…The design of effective surfactants is a key factor in the formation of stable C/W emulsions as well as polymerization of C/W HIPEs . In this regard, many researchers have exploited various surfactants for the stabilization of C/W emulsions and the polymerization of C/W HIPEs, but only some fluorinated and hydrocarbon surfactants have been used successfully …”

Section: Introductionmentioning

confidence: 99%

“…Ammonium perfluoropolyether (PFPE‐NH 4 ) was successfully used to form stable C/W HIPEs, which was then employed to prepare porous polyacrylamide (PAM) matrixes, dextran‐based biocompatible poly‐HIPEs, and highly porous calcium alginate hydrogels with the help of poly(vinyl alcohol) (PVA) as cosurfactant . Several synthetic sugar‐based fluorinated glycol surfactants have also been investigated for the straightforward fabrication of PAM poly‐HIPEs and poly(ionic liquid) monoliths without any cosurfactant . However, fluorinated surfactant is expensive, toxic, and environmentally hazardous.…”

Section: Introductionmentioning

confidence: 99%

“…To date, nearly all efforts have been devoted to exploring the factors that affect the cellular structure and morphology of poly‐HIPEs in the C/W HIPE template polymerization process, but few studies have investigated controlling the mechanical strength of the resulting poly‐HIPEs. To our knowledge, only Boyère et al . reported a postmodification of poly(methyl methacrylate) (PMMA)‐loaded poly‐HIPEs by performing an MMA dispersion polymerization in scCO 2 within the cavities of a cellular PAM scaffold, which allowed an increase in the compressive modulus of the PAM poly‐HIPEs.…”

Section: Introductionmentioning

confidence: 99%

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Preparation of acrylamide‐based poly‐HIPEs with enhanced mechanical strength using PVDBM‐b‐PEG‐emulsified CO₂‐in‐water emulsions

Wang

Liu

et al. 2018

J of Applied Polymer Sci

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Poly(vinyl acetate-alt-dibutyl maleate)-block-poly(ethylene glycol) (PVDBM-b-PEG) copolymers were synthesized via reversible addition-fragmentation chain transfer radical polymerization and used as emulsifiers to form stable CO 2 -in-water high internal phase emulsions (C/W HIPEs). Then, highly interconnected cellular polyacrylamide (PAM) and poly(acrylamide-co-N-hydroxymethyl acrylamide) [P(AM-co-HMAM)] poly-HIPEs with enhanced mechanical strength were prepared based on the stable C/W HIPEs. The porous structures of the PAM poly-HIPEs, as well as morphology and compressive modulus, could be influenced by the surfactant concentration and the length of the CO 2 -philic tails of the surfactants. PAM poly-HIPEs with the smallest average pore diameter (11.12 6 0.62 lm) and the highest compressive modulus (22.65 6 0.10 MPa) could be obtained by using the short CO 2 -philic chains of the PVDBM-b-PEG surfactant at a high concentration (1.0 wt %). Moreover, with the copolymerization of N-hydroxymethyl acrylamide (HMAM) comonomers with acrylamide, the compressive modulus of the obtained P(AM-co-HMAM) poly-HIPEs was three times higher than that of PAM poly-HIPEs. Both PAM and P(AM-co-HMAM) poly-HIPEs were employed as scaffolds to guide H9c2 cardiac muscle cellular growth. Fluorescence images showed that a smaller average pore size and a narrower pore-size distribution were helpful for cell growth and proliferation on these materials. INTRODUCTIONHigh internal phase emulsions (HIPEs, internal phase volume >74.05%) are of great interest in the synthesis of porous organic polymers (poly-HIPEs) by polymerizing the monomers dissolved in the external phase. 1 Removing the internal phase of HIPEs gives poly-HIPEs an open-cell and highly interconnected pore network structure. 2 Due to their advantages of high permeability, uniform cellular structure, easy preparation, and facile control of pore size, poly-HIPEs have been widely discussed as supports for catalysts, 3-5 scaffolds for cell culture, 6,7 and separation media 8 over the last several decades. Poly-HIPEs can be prepared from different HIPEs, such as water-in-oil (W/O) HIPEs, oil-in-water (O/W) HIPEs, and CO 2 -in-water (C/W) HIPEs. 9-11 Among these HIPEs, the C/W HIPE templating method is a green and facile approach, where the internal phase (CO 2 ) can be easily removed by simply depressuring the system. Meanwhile, no volatile organic compounds (VOCs) are used in the process, which makes it suitable for the synthesis of biocompatible materials like cell scaffolds. As we know, the porosity, interconnectivity, and pore size can significantly affect the transport issues of cell scaffolds, including cell migration, nutrient delivery, waste removal, and exclusion of materials or cells. 12 Nevertheless, CO 2 has a poor capability for dissolving most polar and macromolecular substances because of its weak polarity. The design of effective surfactants is a key factor in the formation of stable C/W emulsions as well as polymerization of C/W HIPEs. 13 In this regard, many research...

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Stabilization of CO₂‐in‐water emulsions with high internal phase volume using PVAc‐b‐PVP and PVP‐b‐PVAc‐b‐PVP as emulsifying agents

Wang

Fang

et al. 2018

J of Applied Polymer Sci

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Two newly-designed hydrocarbon surfactants, that is, poly(vinyl acetate)-block-poly(1-vinyl-2-pyrrolidone) (PVAc-b-PVP) and PVP-b-PVAc-b-PVP, were synthesized using reversible addition-fragmentation chain transfer polymerization and used to form CO 2 /water (C/W) emulsions with high internal phase volume and good stability against flocculation and coalescence up to 60 h. Their structures were precisely determined by nuclear magnetic resonance, gel permeation chromatography, thermal gravimetric analysis, and differential scanning calorimetry. Besides low temperature and high CO 2 pressure, the surfactant structures were the key factors affecting the formation and stability of high internal phase C/W emulsions, including the polymerization degrees of CO 2 -philic block (PVAc) and hydrophilic block (PVP), as well as the number of hydrophilic tail. The surface tension of the surfactant aqueous solution and the apparent viscosity of the C/W emulsions were also measured to characterize the surfactants efficiency and effectiveness. The surfactants with double hydrophilic tails showed stronger emulsifying ability than those with single hydrophilic tail. The great enhancement of the emulsions stability was due to decrease of the interface tension as well as increase of the steric hindrance in the water lamellae, preventing a frequent collision of CO 2 droplets and their fast coalescence. V C 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46351.

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Synthesis of microsphere-loaded porous polymers by combining emulsion and dispersion polymerisations in supercritical carbon dioxide

Cited by 16 publications

References 31 publications

High‐Performance Composite Monolith Synthesized via HKUST‐1 Stabilized HIPEs and Its Adsorptive Properties

High‐Performance Composite Monolith Synthesized via HKUST‐1 Stabilized HIPEs and Its Adsorptive Properties

Preparation of acrylamide‐based poly‐HIPEs with enhanced mechanical strength using PVDBM‐b‐PEG‐emulsified CO₂‐in‐water emulsions

Stabilization of CO₂‐in‐water emulsions with high internal phase volume using PVAc‐b‐PVP and PVP‐b‐PVAc‐b‐PVP as emulsifying agents

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Synthesis of microsphere-loaded porous polymers by combining emulsion and dispersion polymerisations in supercritical carbon dioxide

Cited by 16 publications

References 31 publications

High‐Performance Composite Monolith Synthesized via HKUST‐1 Stabilized HIPEs and Its Adsorptive Properties

High‐Performance Composite Monolith Synthesized via HKUST‐1 Stabilized HIPEs and Its Adsorptive Properties

Preparation of acrylamide‐based poly‐HIPEs with enhanced mechanical strength using PVDBM‐b‐PEG‐emulsified CO2‐in‐water emulsions

Stabilization of CO2‐in‐water emulsions with high internal phase volume using PVAc‐b‐PVP and PVP‐b‐PVAc‐b‐PVP as emulsifying agents

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Product

Resources

About

Preparation of acrylamide‐based poly‐HIPEs with enhanced mechanical strength using PVDBM‐b‐PEG‐emulsified CO₂‐in‐water emulsions

Stabilization of CO₂‐in‐water emulsions with high internal phase volume using PVAc‐b‐PVP and PVP‐b‐PVAc‐b‐PVP as emulsifying agents