Synthesis and Characterization of Copolymers and Nanocomposites from Limonene, Styrene and Organomodified-Clay Using Ultrasonic Assisted Method.

In the present work, we report a simple synthesis method for preparation of copolymers and nanocomposites from limonene and styrene using clay as a catalyst. The copolymerization reaction is carried out by using a proton exchanged clay as a catalyst called Mag-H+. The effect of temperature, reaction time and amount of catalyst were studied, and the obtained copolymer structure (lim-co-sty) is characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (1H-NMR) and differential scanning calorimetry (DSC). The molecular weight of the obtained copolymer is determined by gel permeation chromatography (GPC) and is about 4500 g·mol-1. The (lim-co-sty/Mag 1%, 3%, 7% and 10% by weight of clay) nanocomposites were prepared through polymer/clay mixture in solution method using ultrasonic irradiation, in the presence of Mag-CTA+ as green nano-reinforcing filler. The Mag-CTA+ is organophilic silicate clay prepared through a direct exchange process, using cetyltrimethylammonuim bromide (CTAB). The prepared lim-co-sty/Mag nanocomposites have been extensively characterized by FT-IR spectroscopy, X-ray diffraction (XRD), scanning electronic microscopy (SEM) and transmission electronic microscopy (TEM). TEM analysis confirms the results obtained by XRD and clearly show that the obtained nanocomposites are partially exfoliated for the lower amount of clay (1% and 3% wt) and intercalated for higher amounts of clay (7% and 10% wt). Moreover, thermogravimetric analysis (TGA) indicated an enhancement of thermal stability of nanocomposites compared with the pure copolymer.

Green Copolymers and Nanocomposites from Myrcene and Limonene Using Algerian Nano-Clay as Nano-Reinforcing Filler.

In this work, we report a new facile method for the preparation of myrcene-limonene copolymers and nanocomposites using a Lewis acid as a catalyst (AlCl3) and organo-modified clay as a nano-reinforcing filler. The copolymer (myr-co-lim) was prepared by cationic copolymerization using AlCl3 as a catalyst. The structure of the obtained copolymer is studied and confirmed by Fourier Transform Infrared spectroscopy, Nuclear Magnetic Resonance spectroscopy, and Differential Scanning Calorimetry. By improving the dispersion of the matrix polymer in sheets of the organoclay, Maghnite-CTA+ (Mag-CTA+), an Algerian natural organophilic clay, was used to preparenanocomposites of linear copolymer (myr-co-lim). In order to identify and assess their structural, morphological, and thermal properties, the effect of the organoclay, used in varyingamounts (1, 4, 7, and 10% by weight), and the preparation process were investigated. The Mag-CTA+ is an organophylic montmorillonite silicate clay prepared through a direct exchange process in which they were used as green nano-reinforcing filler. The X-ray diffraction of the resulting nanocomposites revealed a considerable alteration in the interlayer spacing of Mag-CTA+. As a result, interlayer expansion and myr-co-lim exfoliation between layers of Mag-CTA+ were observed. Thermogravimetric analysis provided information on the synthesized nanocomposites' thermal properties. Fourier transform infrared spectroscopy and scanning electronic microscopy, respectively, were used to determine the structure and morphology of the produced nanocomposites (myr-co-lim/Mag). The intercalation of myr-co-lim in the Mag-CTA+ sheets has been supported by the results, and the optimum amount of organoclay needed to create a nanocomposite with high thermal stability is 10% by weight. Finally, a new method for the preparation of copolymer and nanocomposites from myrcene and limonene in a short reaction time was developed.

Green Nanocomposites from Rosin-Limonene Copolymer and Algerian Clay.

Green nanocomposites from rosin-limonene (Ros-Lim) copolymers based on Algerian organophilic-clay named Maghnite-CTA+ (Mag-CTA+) were prepared by in-situ polymerization using different amounts (1, 5 and 10% by weight) of Mag-CTA+ and azobisisobutyronitrile as a catalyst. The Mag-CTA+ is an organophilic montmorillonite silicate clay prepared through a direct exchange process; the clay was modified by ultrasonic-assisted method using cetyltrimethylammonuim bromide in which it used as green nano-filler.The preparation method of nanocomposites was studied in order to determine and improve structural, morphological, mechanical and thermal properties ofsin.The structure and morphology of the obtained nanocomposites(Ros-Lim/Mag-CTA+) were determined using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electronic microscopy and transmission electronic microscopy. The analyses confirmed the chemical modification of clay layers and the intercalation of rosin-limonene copolymer within the organophilic-clay sheets. An exfoliated structure was obtained for the lower amount of clay (1% wt of Mag-CTA+), while intercalated structures were detected for high amounts of clay (5 and 10% wt of Mag-CTA+). The thermal properties of the nanocomposites were studied by thermogravimetric analysis (TGA) and show a significant improvement inthe thermal stability of the obtained nanocomposites compared to the purerosin-limonene copolymer (a degradation temperature up to 280 °C).

Ultrasound-induced synthesis of an imidazolium based poly(ionic liquid) in an aqueous media: A structural, thermal and morphological study.

Here we describe an efficient and rapid way for the polymerization of the 3-Octyl-1-vinylimidazolium Bromide using ultrasonic irradiation. This way promoted high dispersion polymerization using a water-soluble free radical initiator namely 4,4'-Azobis (4-cyanopentanoic acid) and free of dispersant. The ionic liquid monomer was prepared via quaternization of 1-vinylimidazole with octyl bromide also promoted by ultrasound. The polymerization rates were compared with a conventional heating method and appeared to be higher in the case of the ultrasound method within a short reaction time. The structural/morphological features and thermal properties of the obtained products were determined by different analytical techniques such as (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), transmission electronic microscopy (SEM, TEM), Fourier transform infrared spectroscopy (FTIR) and NMR Spectroscopy (1H and 13C NMR). The morphology and the thermal behavior of the obtained poly(ionic liquid) were investigated and discussed. The results indicated that self-assembled nanospherical particles of 30-80 nm in diameter were obtained through the ultrasound method, while on the other hand; worm-like/cylindrical agglomerated nanoparticles with irregular sizes 50-300 nm in diameter were obtained via the classical heating method.

Structural, morphological and thermal properties of nanocomposites poly(GMA)/clay prepared by ultrasound and in-situ polymerization.

This work focuses on the preparation and characterization of nanocomposites poly(glycidylmethacrylate)/organoclay. Effect of the organoclays nature and the preparation method were investigated in order to evaluate their structural, morphological and thermal properties. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), nitrogen sorption at 77 K, scanning and transmission electronic microscopy (SEM, TEM) and thermogravimetric analysis (TGA) were employed to determine the features of the obtained materials. In the first step, the Algerian clay was modified by ultrasonic-assisted method using different concentrations of CTAB or TBAHS in which were used as green nano-filler. A series of nanocomposites were prepared by two different methods. The first deals the in-situ polymerization of GMA within the organoclay galleries and the second pathway involves the use of solution blending of poly(GMA) assisted by ultrasound. The obtained results confirm the intercalation of surfactants within the clay layers, while the nanocomposites obtained by the both methods showed different morphologies and structures in which the exfoliated and intercalated forms were obtained. Both nanocomposites displayed significant enhancement in the thermal stabilities compared to the unmodified poly(GMA). The best results in terms of reaction time, clay dispersion and nanocomposite yield were obtained by the ultrasound method.