Molecularly imprinted polymer grafted to porous polyethylene frits: a new selective solid-phase extraction format

In this paper, a novel format for selective solid-phase extraction based on a molecularly imprinted polymer (MIP) is described. A small amount of MIP has been synthesized within the pores of commercial polyethylene (PE) frits and attached to its surface using benzophenone (BP), a photo-initiator capable to start the polymerisation from the surface of the support material. Key properties affecting the obtainment of a proper polymeric layer, such as polymerisation time and kind of cross-linker were optimised. The developed imprinted material has been applied as a selective sorbent for cleaning extracts of thiabendazole (TBZ), as model compound, from citrus samples. The use of different solvents for loading the analyte in the imprinted frits was investigated, as well as the binding capacity of the imprinted polymer. Imprinted frits showed good selectivity when loads were performed using toluene and a linear relationship was obtained for the target analyte up to 1000 ng of loaded analyte. Prepared composite material was applied to the SPE of TBZ in real samples extracts, showing an impressive clean-up ability. Calibrations showed good linearity in the concentration range of 0.05-5.00 μg g(-1), referred to the original solid sample, and the regression coefficients obtained were greater than 0.996. The calculated detection limit was 0.016 μg g(-1), low enough to satisfactory analysis of TBZ in real samples. RSDs at different spiking levels ranged below 15% in all the cases and imprinted frits were reusable without loss in their performance.     

LIVING/CONTROLLED GRAFTING FROM POLYMER MICROSPHERES

A review is given of grafting-from methods using living polymerizations, with emphasis on grafting from polymermicrospheres using ATRP.     

Thermal Behavior of an Fe(III)‐2,9,16,23‐Tetramidephthalocyanine‐Grafted Poly(N‐Vinylcarbazole)

Abstract

The introduction of 2,9,16,23‐tetramide‐Fe(III)phthalocyanine [Fe(III)taPc] units into phosphorylated poly(N‐vinylcarbazole) yields an amorphous grafted polymer containing free carbazolyl groups, phosphonic acid attached to carbazolyl groups, and grafted Fe(III)taPc units as evidenced by infrared spectroscopy. Several thermal transitions were detected by differential scanning calorimetry (DSC). The thermodegradation of the grafted sample, analyzed by simultaneous thermogravimetry‐differential thermal analysis (TG‐DTA), showed successive endo‐ and exothermal reactions resulting from the development of a cross‐linked structure. To determine kinetic parameters, both isothermal and dynamic experiments were performed at the different steps of the degradation process and theoretical methods were applied.     

Thermal transitions and degradative processes in Fe(III)-tetracarboxyphthalocyanine-grafted poly(N-vinylcarbazole)

The introduction of 2,9,16,23-tetracarboxy-Fe(III)phthalocyanine [Fe(III)tcPc] units onto fractions of poly(N-vinylcarbazole) (PVK) by Friedel-Crafts reaction leads to amorphous PVK-based grafted compounds that show major interchain distances by the wide-angle x-ray scattering (WAXS) technique. Glass transition temperatures of the products are lower than the main glass transition temperature of PVK and are attributed to local movements of the voluminous added groups. Dynamic thermogravimetric experiments show decarboxylation processes within the 250°C-500°C range and little weight loss. The large remaining residue, up to 70% of the sample at 800°C, is suggested to be the consequence of successive cross-linking reactions. The Fourier transform infrared (FTIR) spectrum of the residue is similar to that of the grafted sample before degradation.     

Effect of flexibility of grafted polymer on the morphology and property of nanosilica/PVC composites

In this study, poly(methyl methacrylate)-grafted-nanosilica (PMMA-g-silica) and a copolymer of styrene (St), n-butyl acrylate (BA) and acrylic acid (AA)-grafted-nanosilica (PSBA-g-silica) hybrid nanoparticles were prepared by using a heterophase polymerization technique in an aqueous system. The grafted polymers made up approximately 50 wt.% of the resulted hybrid nanoparticles which showed a spherical and well-dispersed morphology. The silica hybrid nanoparticles were subsequently used as fillers in a poly(vinyl chloride) (PVC) matrix to fabricate PVC nanocomposite. Morphology study of PVC nanocomposites revealed that both PMMA- and PSBA-grafted-silica had an adhesive interface between the silica and PVC. The tensile strength and elongation to break were found to be improved significantly in comparison with that of untreated nanosilica/PVC composites. Finally our results clearly demonstrated that the properties (e.g. chain flexibility, composition) of the grafted polymer in the hybrid nanoparticles could significantly affect the dispersion behavior of hybrid nanoparticles in PVC matrix, dynamic mechanical thermal properties and mechanical properties of the resulted PVC composites.     

Molecular structure and properties of cellulose acetate chemically modified with caprolactone

Cellulose acetate (CA) with a degree of substitution of 1.7 was modified with caprolactone (CL) under various reaction conditions in an internal mixer. Processing temperature changed from 120 to 220 °C, while reaction time varied between 5 and 45 min. The composition and structure of the polymer was analyzed by various methods including FTIR, MALDI-TOF and NMR spectroscopy and its mechanical characteristics were determined by dynamic mechanical analysis and tensile testing. The results indicate that homopolymerization occurs under relatively mild conditions, while grafting requires higher temperatures and longer times. Grafted polycaprolactone (gPCL) chains are attached mainly to positions 2 and 6 of the glucose ring and their length increases with increasing reaction time and temperature, but the chains are always much shorter than those obtained in solution polymerization. Changes in the degree of substitution during grafting are small indicating that homopolymerization proceeds easier than grafting. Grafting seems to be easier in cellulose acetate with a larger degree of substitution in spite of the smaller number of active -OH groups present. Internal plasticization is more efficient than the external plasticizing effect of monomeric caprolactone. Plasticization results in a decrease of stiffness and strength, but deformability increases only slightly.     

Cellulose surface grafting with polycaprolactone by heterogeneous click-chemistry

This work deals with a new approach of grafting cellulose surface fibres by polycaprolactone macromolecular chains in heterogeneous conditions via click-chemistry. Thus, cellulose esters were prepared by reacting Avicel with undecynoic acid, in order to prepare cellulose substrate bearing multiple CC-terminated hairs. The prepared modified Avicel substrates were characterised by FTIR, XPS spectroscopy, elemental analyses and showed that the grafting have indeed occurred. The degree of substitution of the prepared cellulose esters was around 0.1. In parallel, polycaprolactone-diol (PCL) was converted to azido-derivative and the ensuing products characterised by FTIR and ¹³C-NMR spectroscopy. Both methods confirmed the success of such modification. Finally, cellulose esters were reacted with azido-PCL grafts in heterogeneous conditions through “click chemistry”. The thus prepared modified cellulose substrates were characterized by FTIR and XPS spectroscopy as well as elemental analyses. The three techniques confirmed the occurrence of the grafting. A weight gain of 20% was achieved.     

Polystyrene/magnesium hydroxide nanocomposite particles prepared by surface-initiated in-situ polymerization

In order to avoid their agglomeration and incompatibility with hydrophobic polystyrene substrate, magnesium hydroxide nanoparticles were encapsulated by surface-initiated in-situ polymerization of styrene. The process contained two steps: electrostatic adsorption of initiator and polymerization of monomer on the surface of magnesium hydroxide. It was found that high adsorption ratio in the electrostatic adsorption of initiator could be attained only in acidic region, and the adsorption belonged to typical physical process. Compared to traditional in-situ polymerization, higher grafting ratio was obtained in surface-initiated in-situ polymerization, which can be attributed to weaker steric hindrance. Both Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) indicated that polystyrene/magnesium hydroxide nanocomposite particles had been successfully prepared by surface-initiated in-situ polymerization. The resulting samples were also analyzed and characterized by means of contact angle testing, dispersibility evaluation and thermogravimetric analysis.     

Controllable synthesis of nanosilica surface-grafted PMMA macromonomers via catalytic chain transfer polymerization

Catalytic chain transfer polymerization (CCTP) has emerged as an efficacious method to produce low-molecular weight polymers. In this paper, we reported the first controllable synthesis of nanosilica surface-grafted poly(methyl methacrylate) (PMMA) (SI-PMMA) macromonomers by using bis(aqua)bis((difluoroboryl)-dimethylglyoximato)cobalt(II) (CoBF) as a chain transfer catalyst via CCTP. In a typical run, we firstly prepared functionalized nanosilica by using 3-(trimethoxysilyl)propylmethacrylate (MPS) as the coupling agent, allowing naosilica containing unsaturated double bonds in end groups. Subsequently, SI-PMMA macromonomers were prepared by PMMA surface-grafted onto the functionalized nanosilica via CCTP. The as-prepared products were characterized by Fourier transforms infrared (FT-IR) spectrum, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transforms Raman (FT-Raman) spectrum and gel permeation chromatography (GPC). We also investigated the dependence of macromonomers on CoBF concentrations.     

Grafting of Poly（lauryl acrylate） onto Nano-silica by ‘Click Chemistry’

Poly（n-alkyl acrylate） with long side groups,namely,poly（lauryl acrylate）（PLA） was synthesized by reversible addition-fragmentation chain transfer（RAFT） polymerization,and the trithioester terminal groups were converted to thiol by reducing reaction.Grafting of the obtained polymer onto nano-silica modified with 3-（methacryloxy）propyl-trimethoxysilane（SiO2-MPS） was conducted by thiol-ene ‘click chemistry＇.PLA was characterized by proton nuclear magnetic resonance（1H NMR） and gel permeation chromatography（GPC）.Fourier transform infrared（FTIR） spectrometry and thermogravimetric analysis（TGA） were used to demonstrate the grafting reaction,and the grafted hairy nano-silica（SiO2-g-PLA） was viewed under a transmission electron microscope（TEM）.According to TGA,grafting ratio and grafting density of SiO2-g-PLA are 30.27％ and 0.013 chain/nm2,respectively.The static water contact angle of SiO2-g-PLA is （80.10±2.97）°,which ensures its hydrophobicity.Dispersion experiment was carried out to confirm its dispersibility in mixed solvents,indicating its potential application in coatings or composites.