Synthesis of chitosan and N-vinylimidazole graft-copolymers and the properties of their aqueous solutions

The aim of this work is to synthesise chitosan and N-vinylimidazole graft-copolymers of various compositions and to study the properties of their aqueous solutions.Chitosan and N-vinylimidazole graft-copolymers were obtained by solution polymerisation in the presence of a ceric ammonium nitrate redox initiator. The synthesised graft copolymers were characterised by FTIR to determine their compositions and the grafted side chains of poly-N-vinylimidazole were characterised by gel permeation chromatography to determine their molecular wights and polydispersity indices. It was established that the obtained products are characterised by high values of yield and grafting efficiency and low values of the polydispersity index. It was found that when the content of the N-vinylimidazole links is above 57 wt%, the synthesised graft copolymers are water-soluble. Aqueous solutions of the obtained copolymers were characterised using dynamic light scattering, transmission electron microscopy, and laserDoppler microelectrophoresis. The study showed that macromolecules of graft copolymers in aqueous solutions have stimuli-sensitive properties with respect to the medium reaction and at a concentration above 10–2 wt% are characterised by a tendency to self-association forming core-crown aggregates, the geometry of which depends on the molecular masses of the grafted chains. Associates of macromolecules in solutions are characterised by positive values of the electrokinetic potential, the values of which also depend on the medium reaction. Thus, it was found that the ceric ammonium nitrate initiator allows obtaining chitosan and N-vinylimidazole graft-copolymers showing stimuli-sensitive properties in aqueous solutions and prone to self-association at concentrations above 10–2 wt%.

Development of Thermally Responsive PolyNIPAm Microcarrier for Application of Cell Culturing—Part I: A Feasibility Study

Poly(N-isopropylacrylamide) (polyNIPAm) microspheres were synthesized via the suspension polymerization technique. Thermal and redox initiators were compared for the polymerization, in order to study the effect of initiator type on the surface charge and particle size of polyNIPAm microspheres. The successful polymerization of NIPAm was confirmed by FTIR analysis. Microspheres of diameter >50 µm were synthesized when a pair of ammonium persulfate (APS) and N,N,N’,N’-tetramethylene-diamine (TEMED) redox initiators was used, whilst relatively small microspheres of ~1 µm diameter were produced using an Azobis-isobutyronitrile (AIBN) thermal initiator. Hence, suspension polymerization using a redox initiator pair was found to be more appropriate for the synthesis of polyNIPAm microspheres of a size suitable for human embryonic kidney (HEK) cell culturing. However, the zeta potential of polyNIPAm microspheres prepared using an APS/TEMED redox initiator was significantly more negative than AIBN thermal initiator prepared microspheres and acted to inhibit cell attachment. Conversely, strong cell attachment was observed in the case of polyNIPAm microspheres of diameter ~90 µm, prepared using an APS/TEMED redox initiator in the presence of a cetyl trimethyl ammonium bromide (CTAB) cationic surfactant; demonstrating that surface charge modified polyNIPAm microspheres have great potential for use in cell culturing.

Synergistic effects in cross-linked blends of ion-conducting PEO-/PPO-based unsaturated polyesters

Ion-conductive unsaturated polyesters (UP) were synthesised from poly(ethylene oxide) (Xn = 9, 13, 22, 90) or poly(propylene oxide) (Xn = 7, 13, 20, 34, 68) and maleic anhydride. Subsequently, the polyesters were doped with LiClO4 and cross-linked with styrene using a redox initiator. For PEO-based polyesters, the minimum resistivity is found at an O/Li+ molar ratio of 50/1. In contrast, more lithium is required to reach the minimum when using PPO (O/Li+ = 10/1). Unlike the PEO-based polyesters, cross-linking of the PPO types gives rise to decreasing resistivities at increasing molecular weight. This correlates well with the transverse proton relaxation time determined by single-sided NMR, which is an indicator of the chain mobility. The cross-linking reaction of these UP with styrene exactly follows the predictions based on the copolymerisation parameters and is, therefore, not dependent on the ratio of styrene to UP double bonds as previously reported. Due to the opposing effects of the molecular weight on the ion conductivity of PEO- and PPO-based UP, 1:1 blends of short-chain PPO and long-chain PEO polyesters were cross-linked with styrene. The resulting networks showed a resistivity of 4 kΩ m (σ = 2.5∙10−4 S∙m−1), which is 5 times lower than the pure PEO and 3 times lower than the pure PPO materials.

Application of Bacterial Cellulose in the Textile and Shoe Industry: Development of Biocomposites

Several studies report the potential of bacterial cellulose (BC) in the fashion and leather industries. This work aimed at the development of BC-based composites containing emulsified acrylated epoxidized soybean oil (AESO) that are polymerized with the redox initiator system hydrogen peroxide (H2O2) and L-ascorbic acid and ferrous sulfate as a catalyst. BC was fermented under static culture. The polymerization of the emulsified organic droplets was tested before and after their incorporation into BC by exhaustion. The composites were then finished with an antimicrobial agent (benzalkonium chloride) and dyed. The obtained composites were characterized in terms of wettability, water vapor permeability (WVP), mechanical, thermal and antimicrobial properties. When AESO emulsion was polymerized prior to the exhaustion process, the obtained composites showed higher WVP, tensile strength and thermal stability. Meanwhile, post-exhaustion polymerized AESO conferred the composite higher hydrophobicity and elongation. The composites finished with the antimicrobial agent showed activity against S. aureus. Finally, intense colors were obtained more uniformly when they were incorporated simultaneously with the emulsified AESO with all the dyes tested.

Research of a novel double cross-linking fracturing fluid

A kind of JDL-1 thickener for betaine hydrophobic association polymer was prepared by aqueous solution polymerization of mixed micelles, AM, AA, AMPS and DM16 were used as raw materials, which was synthesized by redox initiator system. Friction tester and high-temperature rheometer were used to evaluate the resistance reduction and temperature and shear resistance of the thickener. The results show that the viscosity average molecular weight of the polymer prepared with AM, AA, AMPS and DM16 mass ratio of 70∶20∶5∶5 was higher than 12 million, and the dissolution time of the polymer was less than 3 min. When the surfactant is used for physical cross-linking, the apparent viscosity of the cross-linked fracturing fluid is larger than that of 60 mPa·s at 90 °C, 170 s-1 sheared 1 h; when metal cross-linking agent is used for coordination cross-linking, the apparent viscosity is larger than that of 80 mPa·s at 120 °C, 170 s-1 sheared 1 h. The drag reduction rate was 73%, the anti-swelling rate was higher than70%, and the damage rate was less than10%. The field trial was successful and confirmed the multifunctional effect of betaine-type hydrophobic associating polymer.

Synthesis and Rheological Survey of Xanthan Gum Based Terpolymeric Hydrogels

Graft copolymerization technique was used to synthesize novel biopolymer based terpolymeric hydrogels of xanthan gum (Gx), acrylic acid and N-Isopropyl acrylamide (NIPAM) by using chemical crosslinker N,N′-methylene bisacrylamide (MBA), ammonium persulphate (APS) as a redox initiator and sodium dodecyl sulphate (SDS) for particle size stabilization. The synthesized hydrogels were characterized through FT-IR and SEM techniques, which confirmed the hydrogels formation. Detailed rheology was investigated through applying various rheological models like Bingham model, modified Bingham model and Ostwald power law model to the hydrogels which revealed that the hydrogels were appeared to have shear thinning, non-Newtonian behavior and more elastic. Modified Bingham model provided best fit understanding to our prepared materials. The maximum activation energy (Ea) 13.87 kJ/mol was obtained for composition having more Gx compared to others, showing a strong relationship with viscosity. The hydrogels has potential to find applications in food industry, cosmetics, degradation of dyes and removal of heavy metals from waste water.

Preparation of high molecular weight polyvinyl alcohol by emulsifier-free emulsion polymerization

In this report, high molecular weight polyvinyl alcohol (PVA) was prepared by emulsifier-free emulsion polymerization, using the redox initiator of potassium persulfate (KPS) / N,N-dimethyl ethanolamine (DMEA). The structure and property of PVA were studied by using ubbelohde viscometer, fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance hydrogen spectroscopy (1H-NMR), X-ray Diffraction (XRD), differential scanning calorimeter (DSC) and thermo gravimetric analysis (TGA). The results showed that the viscosity-average degree of polymerization (DP) of PVA 7506, which was much higher than that of PVA commonly used in industrial production. The syndiotacticity and crystallinity of PVA was 54.2 % and 35.6 %, respectively.

Super Effective Removal of Toxic Metals Water Pollutants Using Multi Functionalized Polyacrylonitrile and Arabic Gum Grafts

Super adsorbent polymers can be considered to be a very efficient solution for wastewater treatment. In general, their adsorption capacities depend on the type and amount of the functional groups present on the surface of the polymers, while their economic value is affected by their cost. Therefore, this study aims to understand the effect of multi-functionalization of cheap Arabic gum on the adsorption capability toward heavy metals. Graft copolymers of polyacrylonitrile (PAN) onto Arabic gum (AG) were prepared in aqueous solution using (KMnO4/HNO3) as a redox initiator. Chemical modification of the graft copolymer was carried out by reaction with hydrazine hydrochloride followed by hydrolysis in the basic medium. The modified graft product was characterized by various techniques, such as Fourier transform infrared spectroscopy (FTIR), elemental analysis, scanning electron microscope (SEM), and X-ray powder diffraction (XRD). The modified graft copolymer was used to adsorb Pb2+, Cd2+ and Cu2+ from their aqueous solutions using batch extraction. Different parameters influence the uptake behavior, including contact time, pH, and the initial concentration of the metal ions; all of these were investigated. The kinetics were investigated using the pseudo first order and pseudo second order, and the equilibrium data were analyzed using the Langmuir and Freundlich model. The modified graft product showed the superadsorbent capacity to obtain maximum values (Qmax) 1017, 413 and 396 mg/g for Pb2+, Cd2+ and Cu2+, respectively. Acid treatment with 0.2 M HNO3 resulted in 96%, 99% and 99% metal recovery for the Pb2+, Cd2+ and Cu2+, respectively. This indicates the recyclability of product for further usage upon drying between treatments.

Study of Synthesis and Flocculation Properties of New Modified Hydrophobic Organic Polymer P(AM-DM-DMC12)

A new modified hydrophobic organic polymer P(AM-DM-DMC12) is synthesized by free radical polymerization of three monomers in aqueous solution using a REDOX initiator system. Its structure is characterized by FT-IR and 1H-NMR, the effect of reaction conditions on the product is studied, and the flocculation performance and mechanism are discussed with the aim of wastewater turbidity and COD removal rate. The results showed that the synthesized compounds accorded with the target structure, and the optimum synthetic conditions are as follows: the molar ratio of AM, DM, and DMC12 is 4 : 1 : 1, total mass fraction of monomer is 35%, the mass fraction of redox initiator is 0.06%, and the molecular weight of P(AM-DM-DMC12) is 1.02×107. Moreover, the flocculation effect of P(AM-DM-DMC12) is obviously better than that of PAM, and it has the advantages of short flocculation time, low dosage, and wide application range of pH and has a good industrial application value and prospect.