ArticlePublisher preview available

1,2,3-triazole functionalized polystyrene and perdeuterated polystyrene chelating latexes

Authors:
To read the full-text of this research, you can request a copy directly from the authors.

Abstract and Figures

Emulsifier-free polystyrene latexes with immobilized triazolic residues have been prepared by batch emulsion copolymerization of styrene with 1,2,3-triazole-based acrylic monomers containing diethylene or triethylene glycol monomethyl ether groups DEGTz and TEGTz, respectively. The effect of monomer structure and concentration on polymerization conversion, particle size, and morphology was investigated. Particle composition was also evidenced by ¹H-NMR analysis. It was found that DEGTz monomer with the shorter pegylated chain allows the formation of the smaller particles with a better control of polytriazole water soluble oligomers formation. DEGTz and TEGTz were then used in batch and shot-growth polymerization of styrene-d8 in the aim to highlight the effect of deuterium isotope substitution. It was shown that the use of deuterated styrene significantly impacts the polymerization conversion as well as particle size and shape regardless of the monomer structure. Shot-growth process disadvantaged the copolymer particle formation in favor of obtaining water soluble polymers. This was confirmed from the NMR study and from the large values of surface charge density of latexes obtained from electrophoretic mobility.
This content is subject to copyright. Terms and conditions apply.
ORIGINAL CONTRIBUTION
1,2,3-triazole functionalized polystyrene and perdeuterated
polystyrene chelating latexes
Hadjira Lahmar
1
&Ibrahim Badr
2
&Chariya Kaewsaneha
2,3
&Abdelhamid Elaissari
2
&Salima Saidi-Besbes
1
Received: 30 January 2019 /Revised: 9 March 2019 /Accepted: 1 April 2019 /Published online: 27 May 2019
#Springer-Verlag GmbH Germany, part of Springer Nature 2019
Abstract
Emulsifier-free polystyrene latexes with immobilized triazolic residues have been prepared by batch emulsion copolymerization
of styrene with 1,2,3-triazole-based acrylic monomers containing diethylene or triethylene glycol monomethyl ether groups
DEGTz and TEGTz, respectively. The effect of monomer structure and concentration on polymerization conversion, particle
size, and morphology was investigated. Particle composition was also evidenced by
1
H-NMR analysis. It was found that DEGTz
monomer with the shorter pegylated chain allows the formation of the smaller particles with a better control of polytriazole water
soluble oligomers formation. DEGTz and TEGTz were then used in batch and shot-growth polymerization of styrene-d8 in the
aim to highlight the effect of deuterium isotope substitution. It was shown that the use of deuterated styrene significantly impacts
the polymerization conversion as well as particle size and shape regardless of the monomer structure. Shot-growth process
disadvantaged the copolymer particle formation in favor of obtaining water soluble polymers. This was confirmed from the
NMR study and from the large values of surface charge density of latexes obtained from electrophoretic mobility.
Keywords 1,2,3-triazole .Chelating monomer .Emulsion polymerization .Perdeuterated polystyrene .Shot-growth process
Introduction
In recent years, the use of polymer supports for immobiliza-
tion of several ligands, catalysis and probes has generated
great interest for organic synthesis, biomedical, and environ-
mental applications [1,2]. The activity of attached reagent is
directly tied to its accessibility to the active sites and is often
limited due the burying of these sites inside the cross-linked
supports. In this context, the development of novel supported
polymers with improved selectivity, efficiency, stability, reac-
tion kinetic, thermal, and mechanical properties is highly re-
quested for products that fulfill customersrequirements.
Several methods have been used to access to such polymers
with controlled functionality, size, and size distribution such
as emulsion polymerization, suspension polymerization, pre-
cipitation polymerization, or atom transfer radical (ATRP) and
reversible addition-fragmentation chain transfer (RAFT) po-
lymerization techniques [35]. Micro- and submicrosized par-
ticles with a broad variety of morphologies can be obtained
that exhibit high surface area to volume ratio helpful for inter-
action with actives sites. Among these methods, emulsion
polymerization has gained its popularity as an easy production
process because of its numerous outstanding advantageous as
good temperature control, high polymerization rate, low vis-
cosity of the final dispersions, and easy removal of unreacted
monomers. Furthermore, the use of emulsifierfree process
allows to prevent the contamination of the final products by
emulsifier and consequently the latex properties deterioration
due to the surfactant migration particularly for coating and
adhesive applications [6,7].
For metal remediation applications, various low-molecular
ligands have been immobilized on polymer matrix. Among
them, those containing nitrogen, oxygen, and phosphorus
atoms received particular attention due to their strong affinity
for divalent transition metal cations. The most common li-
gands include heterocyclic amines, amidoximes, dithizone,
*Salima Saidi-Besbes
saidi.salima@univ-oran1.dz
1
Laboratoire de Synthèse Organique Appliquée (LSOA),
Département de Chimie, Faculté des Sciences Exactes et Appliquées,
Université Oran1, Bp 1524 El Mnaouer, 31000 Oran, Algeria
2
CNRS, LAGEP-UMR 5007, Univ Lyon, University Claude Bernard
Lyon-1, F-69622 Lyon, France
3
School of Bio-Chemical Engineering and Technology, Sirindhorn
International Institute of Technology (SIIT), Thammasat University,
PathumThani 12121, Thailand
Colloid and Polymer Science (2019) 297:11191131
https://doi.org/10.1007/s00396-019-04509-2
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
... These are defined by membrane physical and chemical properties process variables, solvent/solute ratio, operating pressure, coagulant bath temperature, organic and inorganic additives. To address the issues of conventional polymeric membranes, nanocomposite membranes have gained significant attention for water purification over the last three decades [2][3][4][5]. ...
Article
Full-text available
Mixed-matrix nanocomposite (PES/CA/PVP) membranes were fabricated for water desalination by incorporating varying amount of titanium dioxide nanoparticles (TiO2 NPs) ranging from 0 and 2 wt. %. Efficient dispersion of nanoparticles within polymeric membranes was achieved using the chemical precipitation method for uniform surface generation, and an asymmetric morphology was achieved via phase inversion method. Finally, membranes were characterized by Fourier Transform Infrared (FTIR) spectroscopy, Thermo Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), porosity and contact angle analysis. FTIR confirmed chemical composition of membranes in terms of polymers (PES/CA/PVP) and TiO2. TGA analysis confirmed an increase in thermal stability of membranes with the increase of TiO2 nanoparticles loading. The addition of TiO2 nanoparticles also resulted in an increase in porous structures due to an increase in mean pore size, as shown by SEM results. An increase in the hydrophilicity of the membranes was observed by increasing the concentration of TiO2 nanoparticles. The present study investigated pristine and mixed-matrix nanocomposite NF membrane performance while filtering a NaCl salt solution at varying concentration range (from 1 to 4 g/Lit 6 bar). The prepared membranes demonstrated significant improvement in water permeability and hydrophilicity. Further, to optimize the water flux and salt rejection, the concentration of Polyvinylpyrrolidone (PVP) was optimized along with TiO2 nanoparticles. Both the water flux and salt rejection of the fabricated membranes were observed to increase with an increase inTiO2 nanoparticles to 2 wt. % loading with optimized PVP concentration, which demonstrated the improved desalination performance of resultant membranes.
Article
Full-text available
The main goal of this work is to investigate the ability of 1,2,3-triazole functionalized magnetic nanoparticles (MNP-Trz) and silica coated MNP homologous (MNPS-Trz) for removal of heavy metal cations. Three steps efficient synthetic pathway were used for chemical modification of magnetic core based on cupper catalyzed 1,3-dipolar cycloaddition. The magnetic nanoparticles were characterized by using various techniques such as X-ray diffraction (WAXD), infrared spectroscopy (FTIR), thermogravimetry analysis (TGA), zeta potential analysis, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The adsorption of prepared nanosized magnetic nanoparticles toward Cu²⁺, Pb²⁺ and Zn²⁺ ions was examined as a function of various physical-chemistry conditions. Adsorption isotherms and kinetics were studied and discussed by considering various theoretical models. The equilibrium kinetics was found to be second order model irrespective of investigated system. The best corroborating model with the obtained experimental results was found to be Langmuir one with maximum adsorption capacities at pH 5.5 and 25°C for Cu²⁺, Pb²⁺ and Zn²⁺ ions found to be 87.87, 167.78 and 51.20 mg.g⁻¹, respectively. Similar high maximum uptake tendency was also obtained for magnetic core-silica shell nanoparticles. It is interesting to notice that the regeneration of the used MNP-Trz was successfully achieved by using 0.1M HNO3 since 88% desorption efficiency was reached.
Article
Full-text available
In this study, monodisperse polystyrene nanospheres were prepared by dispersion polymerization using alcohol as reaction medium to prepare colloidal clusters of the latex beads. Polyvinylpyrrolidone (PVP) and 2-(methacryloyloxy)ethyltrimethylammonium chloride (MTC) were used as dispersion stabilizer and comonomer, respectively. The particle size could be controlled by adjusting the reactant compositions such as the amount of stabilizer, comonomer, and water in the reactant mixture. The size and monodispersity of the polymeric particles could be also controlled by changing the reaction medium with different alcohols other than ethanol or adjusting the polymerization temperature. The synthesized particles could be self-organized inside water-in-oil emulsion droplets by evaporation-driven self-assembly to produce colloidal clusters of the polymeric nanospheres.
Article
A new impedimetric immunosensor was fabricated for detection of Interleukin 1β (IL-1β) by using semi-conductive poly(2-thiophen-3-yl-malonic acid) (P3-TMA) as an immobilization matrix material and anti-IL-1β antibody as a biorecognition element for the first time. The polymer P3-TMA bound onto hydroxylated ITO surface via ester bond to form a polymer interface including active carboxyl groups. These reactive carboxyl groups bound to anti-IL-1β antibodies via amide bond under coupling reagent of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride/N-hydroxysuccinimide. The detection of IL-1β antigen was monitored with electrochemical impedance spectroscopy technique (EIS). Apart from EIS technique, cyclic voltammetry (CV), fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), SEM-energy dispersive X-ray (EDX) mapping, atomic force microscopy (AFM) were used for characterization of immunosensor. The effect of antibody and antigen incubation durations, and utilized biorecognition element concentrations were investigated to determine the optimum analytical performance of the immunosensor. Under optimized conditions, the relative change in impedance was proportional to the IL-1β concentration in the range of 0.01–3 pg/mL with the detection limit 3 fg/mL. The proposed immunosensor had good specificity, reproducibility and stability. The immunosensor was applicable for detection of IL-1β in human serum and saliva samples with satisfied recoveries (97.4–104.5%).
Article
Achiral polymeric supports can have important positive effects on the activity, stability and selectivity of supported chiral catalysts.
Article
We prepared submicrometer-sized polystyrene (PS) particles by emulsion polymerization with/without polyoxyethylene nonylphenyl ether nonionic emulsifier (Emulgen 911), and examined how water absorption was affected by polymer end-groups derived from hydrophilic (ionic) or hydrophobic (nonionic) initiator and/or incorporated nonionic emulsifier when they were inside these particles. PS particles having sulfate end-groups, which were prepared using potassium persulfate initiator with/without Emulgen 911, absorbed a certain amount of water inside them, whereas those having isobutyronitrile end-groups derived from 2,2’-azobis(isobutyronitrile) initiator did not. Absorption of water inside the particles caused by the incorporated Emulgen 911 alone was minimal in the absence of the sulfate end-groups. Considering that sulfate end-groups existing at the particle surface do not contribute to water absorption into the particles, these results indicate that sulfate end-groups did not only exist at the surface of the PS particles but were also buried inside the PS particles during the emulsion polymerization. This offers a clear explanation of a longtime enigma in (emulsifier-free) emulsion polymerization. Both the ionic end-groups buried in the particles and the nonionic emulsifier incorporated inside cooperate to absorb water, thus resulting in the formation of hollow PS particles.
Article
The effects of deuterium isotope substitution on conjugated polymer chain stacking of poly(3-hexylthiophene) is studied experimentally by X-ray diffraction (XRD) in combination with gel permeation chromatography and theoretically using density functional theory and quantum molecular dynamics. For four P3HT materials with different levels of deuteration (pristine, main-chain deuterated, side-chain deuterated, and fully deuterated), the XRD measurements show that main-chain thiophene deuteration significantly reduces crystallinity, regardless of the side-chain deuteration. The reduction of crystallinity due to the main-chain deuteration is a quantum nuclear effect resulting from a static zero-point vibrational energy combined with a dynamic correlation of the dipole fluctuations. The quantum molecular dynamics simulations confirm the inter-chain correlation of the proton-proton and deuteron-deuteron motions, but not of the proton-deuteron motion. Thus, isotopic purity is an important factor affecting stability and properties of conjugated polymer crystals, which should be considered in the design of electronic and spintronic devices.
Article
Submicrometer-sized raspberry-like polystyrene (PS) particles prepared by emulsion polymerization with polyoxyethylene nonylphenyl ether nonionic emulsifier (Emulgen 910, HLB 12.2) was incorporated 5.5 wt% (relative to PS) of Emulgen 910 and contained 8.5 vol% (relative to particle) of water in the inside. The water absorption decreased the glass transition temperature of PS particles dispersed in an aqueous medium. The wt% (relative to PS) of incorporated Emulgen 910 increased with increasing initial Emulgen 910 concentration in the emulsion polymerization but wt% (relative to total Emulgen 910 used) of the incorporated Emulgen 910 was constant at approximately 50% independently of the initial concentration. The vol% (relative to particle) of water was increased to 46% by heat treatment at 90 ˚C for 24 h, which was based on further water absorption, and resulted in spherical hollow particles. Where, the amount of incorporated Emulgen 910 remarkably decreased in a short treatment, and then remained almost constant during the heat treatment. After another 24 h treatment, the percentage of non-hollow particles increased gradually, which was based on an escaping of the water domain together with Emulgen 910 from the inside of the particles. On the other hand, spherical PS particles prepared by emulsifier-free emulsion polymerization did not contain water in the inside and were not changed to hollow ones by a similar heat treatment. From these results, an innovative easy method to synthesize hydrophobic hollow PS particles is proposed.
Article
This work aims to prepare polymer latex particles bearing chelating compound. Latex particles were prepared via emulsion polymerization process using the functional monomer as the main monomer. The prepared functional monomer was characterized in terms of NMR analysis. UV-visible and FTIR spectroscopies were used to investigate the chelating properties of a novel polymeric agent based on 1,2,3-triazole acrylic derivative. Stability constants and average coordination numbers were determined by applying the molar ratio method. Results indicate that one metal ion is coordinated by two triazole units. The prepared polytriazole polymer forms stable complexes in the following metal ion affinity order: Cu2+ > Ni2+ > Co2+.
Article
A ‘shot growth’ technique has been developed which enables a monodisperse polymer latex to be overcoated with a range of coating thicknesses by a different polymer. This has enabled a range of polymer latices to be produced which have mechanical and diffusional characteristics which are very different from either the seed latex or the coating polymer.