Synthesis and characterization of hydroxypropyl methylcellulose and ethyl acrylate graft copolymers

The synthesis of hydroxypropyl methylcellulose-g-poly (ethyl acrylate) was carried out by potassium persulfate induced graft copolymerization in homogeneous aqueous medium. By varying the reaction conditions, graft copolymers with different percentage of grafting were prepared. These graft copolymers were characterized by fourier transform infrared spectra (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analyses (TGA), X-ray diffraction analysis (XRD), and dynamic light scattering (DLS) methods. The molecular weight of grafted and ungrafted polymer chains determined by gel permeation chromatography (GPC) increased with increasing monomer and matrix concentration but decreased with increasing initiator concentration and reaction temperature. The mechanical properties of graft copolymers were measured as function of the percentage of grafting. In addition, the equilibrium humidity adsorption behavior and the disintegration time of the grafted copolymer films were also studied.     

Poly(ethylene glycol)-carboxymethyl chitosan-based pH-responsive hydrogels: photo-induced synthesis, characterization, swelling, and in vitro evaluation as potential drug carriers

In this study, carboxymethyl chitosan was prepared, characterized, and then photo-induced graft copolymerized with poly(ethylene glycol) under a nitrogen atmosphere in aqueous solution using 2,2-dimethoxy-2-phenyl acetophenone (DMPA) as the photo-initiator. The grafting copolymerization process was confirmed and the resulting copolymers were characterized using differential scanning calorimetry (DSC), FTIR spectroscopy, 2D-X ray diffraction, and elemental analysis. The kinetics of the grafting reactions was also studied. Under the applied experimental conditions, the optimum grafting values were obtained at: CMCs = 0.2 g, PEGA = 249 mM, DMPA = 10.4 mM at a 2 h reaction time. Some of the resulting copolymers were selected and used in the presence of methylene bisacrylamide (MBA) as a crosslinking agent to develop pH-responsive hydrogel matrices. The swelling characteristics and the in vitro release profiles of 5-fluorouracil (5-FU), as a model drug, from the hydrogels were investigated. The results revealed that the hydrogel matrices developed in this study can be customized to act as good candidates in drug delivery systems.     

Crystallization behavior and hydrophobic properties of biodegradable ethyl cellulose-g-poly(3-hydroxybutyrate-co-3-hydroxyvalerate): The influence of the side-chain length and grafting density

The copolymerization of grafting poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) onto ethyl cellulose (EC) was carried out through the homogeneous acylation reaction between EC as a backbone and telechelic OH-terminated PHBV oligomer as side chains in 1,2-dichloroethane by using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent and dibutyltin dilaurate as catalyst. The resulting copolymers were studied by using NMR, FT-IR, WAXD, DSC, and contact angle measurements. It is found that with the increasing of the HDI/PHBV fraction, a transition exhibition occurred on crystallization behavior and hydrophobic properties, which could be modulated through controlling the lengths and grafting densities of PHBV side chains. Compared with those of neat PHBV, the degree of crystallinity for EC-g-PHBV_1.8 decreased from 58.1% to 39.1%, the maximum decomposition temperature increased from 259.6 to 266.3 °C, and the contact angle increased from 60.1° to 95.7°.     

Graft copolymerization of ethyl acrylate onto cellulose using ceric ammonium nitrate as initiator in aqueous medium

Ceric ammonium nitrate (CAN) in the presence of nitric acid has been used as efficient initiator for graft copolymerization of the ethyl acrylate onto cellulose at 35.0 +/- 0.1 degrees C. Graft copolymerization of ethyl acrylate onto cellulose has taken place through the radical initiation process. The graft yield and other grafting parameters have been evaluated by varying concentration of ethyl acrylate from 2.5 x 10(-1) to 15.0 x 10(-1) mol dm(-3) and ceric ammonium nitrate from 5.0 x 10(-3) to 25.0 x 10(-3) mol dm(-3) at constant concentration of the nitric acid (8.0 x 10(-2) mol dm(-3)). The rate of graft copolymerization has shown 1.5 order with respect to the concentration of the ceric ammonium nitrate. The graft copolymerization data obtained at different temperatures were used to calculate the energy of activation, which has been found to be 28.9 kJ mol(-1) within the temperature range from 20 to 50 degrees C. The effect of addition of cationic and anionic surfactants on graft copolymerization has also been studied. On the basis of the experimental observations, reaction steps have been proposed and a suitable rate expression for graft copolymerization has been derived.     

Adsorption of chromium and zinc ions from aqueous solutions by cellulosic graft copolymers

Cellulosic graft copolymers were prepared by the reaction of bast fibers of the kenaf plant (Hibiscus cannabinus) with acrylonitrile and methacrylonitrile monomers in aqueous media initiated by the ceric ion-toluene redox pair. The cellulose-polyacrylonitrile (Cell-PAN) and cellulose-polymethacrylonitrile (Cell-PMAN) graft copolymers were used for the removal of Zn(II) and Cr(III) ions from aqueous solutions at 30°C. Zn(II) ion was more sorbed than Cr(III) ion by both copolymers by an average factor of 1.80 ± 0.40. For each metal ion, the Cell-PAN graft copolymer was a more effective sorbent than the Cell-PMAN derivative. The amount of ion sorbed decreased with an increase in percentage graft and over the range 38–149% of the graft the amounts of Zn(II) and Cr(III) ions sorbed by Cell-PAN decreased by 44% and 56%, respectively.     

Radiation-induced eco-compatible sulfonated starch/acrylic acid graft copolymers for sucrose hydrolysis

Radiation-induced graft-copolymers capable of hosting sulfonic groups and having more effective catalytic activity towards sucrose hydrolysis were prepared. Acrylic acid monomer (AA) was copolymerized with sulfonated starch (SS) at different compositions using ionizing radiation. Swelling behavior of the prepared copolymers at different environmental conditions was studied as well as thermal stability. The hydrolysis of sucrose to glucose and fructose by sulfonated starch/acrylic acid (SS/AA) graft copolymers was investigated. The kinetics of the reaction was determined for various (SS/AA) graft copolymers compositions and at a temperature range of 40-60 °C. The catalytic activity of the copolymers was found to be dependent on the reaction temperature and (SS/AA) graft copolymers compositions, it increases as the reaction temperature and sulfonated starch content (in the feed solution) increases. The obtained results suggest that the prepared SS/AA copolymers could be considered as catalytic reagent for sucrose hydrolysis.     

Synthesis, characterization and thermal sensitivity of chitosan-based graft copolymers

Novel chitosan-based graft copolymers (CECTS-g-PDMA) were synthesized through homogeneous graft copolymerization of (N,N-dimethylamino)ethyl methacrylate (DMA) onto N-carboxyethylchitosan (CECTS) in aqueous solution by using ammonium persulfate (APS) as the initiator. The effect of polymerization variables, including initiator concentration, monomer concentration, reaction time and temperature, on grafting percentage was studied. XRD, FTIR, DSC and TGA were used to characterize the graft copolymers. Surface-tension measurements, turbidity measurements and temperature-variable (1)H NMR analysis were combined to investigate the thermal sensitivity of CECTS-g-PDMAs in aqueous solution.     

Novel organo-mineral phases obtained by intercalation of maleic anhydride-allyl ether copolymers into layered calcium aluminum hydrates

The work presented here deals with the intercalation of worm- and brush-shaped polycarboxylates (PC) into calcium aluminum layered double hydroxide (Ca-Al-LDH). The nanocomposite materials were obtained from tricalcium aluminate hydration in presence of polycarboxylate copolymers with different side chain lengths. As polycarboxylate compound, amphiphilic copolymers composed of maleic anhydride and α-allyl-ω-methoxy-poly(ethylene glycol) ether with side chain lengths of n = 7, 10, 34, 70 and 90 ethylene oxide units (EOUs) were chosen. These polymers possess a high side chain density due to strictly alternating copolymerization. Powder X-ray diffraction (XRD) of the synthesized Ca-Al-PC-LDH composites revealed that basal spacings (d-values) increase with the number n of EOUs in the side chain. An extremely high d-value of 4.85 nm was obtained for the polymer with n = 34 EOUs. According to elemental analysis data, the amounts of organic material present in the different composites were found to lie between 48 and 77 wt.%, respectively. Additionally, IR spectroscopy and thermogravimetric measurements were carried out in order to characterize the intercalates. The layered structure of the organo-mineral materials was confirmed by transmission electron microscopy (TEM).     

A comparative study on the graft copolymerization of acrylic acid onto rayon fibre by a ceric ion redox system and a γ-radiation method

Functionalization of rayon fibre has been carried out by grafting acrylic acid (AAC) both by a chemical method using a Ce⁴⁺-HNO₃ redox initiator and by a mutual irradiation (γ-rays) method. The reaction conditions affecting the grafting percentage have been optimized for both methods, and the results are compared. The maximum percentage of grafting (50%) by the chemical method was obtained utilizing 18.24 × 10⁻³ moles/L of ceric ammonium nitrate (CAN), 39.68 × 10⁻² moles/L of HNO₃, and 104.08 × 10⁻² moles/L of AAc in 20 mL of water at 45 °C for120 min. For the radiation method, the maximum grafting percentage (60%) was higher, and the product was obtained under milder reaction conditions using a lower concentration of AAc (69.38 × 10⁻² moles/L) in 10 mL of water at an optimum total dose of 0.932 kGy. Swelling studies showed higher swelling for the grafted rayon fibre in water (854.54%) as compared to the pristine fibre (407%), while dye uptake studies revealed poor uptake of the dye (crystal violet) by the grafted fibre in comparison with the pristine fibre. The graft copolymers were characterized by IR, TGA, and scanning electron micrographic methods. Grafted fibre, prepared by the radiation-induced method, showed better thermal behaviour. Comparison of the two methods revealed that the radiation method of grafting of acrylic acid onto rayon fibre is a better method of grafting in comparison with the chemical method.     

Xanthan-g-poly(acrylamide): Microwave-assisted synthesis,characterization and in vitro release behavior

Xanthan-g-poly(acrylamide) was synthesized employing microwave-assisted and ceric-induced graft copolymerization, and was characterized by FT-IR, DSC, XRD and SEM studies. Matrix tablets of diclofenac sodium were formulated using graft copolymer as the matrix by direct compression technique. Release behavior of the graft copolymer was evaluated using USP type-II dissolution apparatus in 900 ml of phosphate buffer (pH 6.8), maintained at 37 °C and at 50 rpm. Microwave-assisted grafting provided graft copolymer with higher % grafting in a shorter time in comparison to the ceric-induced grafting. The % grafting was found to increase with the increase in the power of microwave and/or time of exposure. The matrix tablets were found to release the drug by zero-order kinetics, and the faster release of drug was observed from the graft copolymer matrix as compared to the xanthan gum matrix. It was observed that grafting reduces the swelling, but increases the erosion of xanthan gum.     

Graft copolymerization of methyl methacrylate onto mercaptochitin and some properties of the resulting hybrid materials

The graft copolymerization of methyl methacrylate onto mercaptochitin and some properties of the resulting graft copolymers have been studied. Methyl methacrylate was efficiently graft copolymerized onto mercaptochitin in dimethyl sulfoxide, and the grafting percentage reached 1300% under appropriate conditions. Although the side-chain ester groups were resistant to aqueous alkali, hydrolysis could be achieved with a mixture of aqueous sodium hydroxide and dimethyl sulfoxide. Subsequent treatment with acetic anhydride in methanol transformed the sodium carboxylate groups into carboxyl groups. Although the graft copolymers exhibited an improved affinity for organic solvents, those having sodium carboxylate or carboxyl units were characterized by a much more enhanced solubility and were soluble in common solvents. The hygroscopic nature of chitin decreased with an increase in the grafting extent but increased significantly upon hydrolysis of the ester groups. The enzymatic degradability of the graft copolymers, as evaluated with lysozyme, was also dependent on the grafting extent and much higher than that of the original chitin. DSC measurements revealed the presence of a glass transition phenomenon, which could be ascribed to the poly(methyl methacrylate) side chain.     

Synthesis, characterization and aqueous dispersion of dextran-g-poly(1,4-dioxan-2-one) copolymers

A novel biodegradable graft copolymer, dextran-g-poly(1,4-dioxan-2-one) (PODEX), was synthesized through the ring-opening polymerization (ROP) of 1,4-dioxan-2-one (PDO) onto a dextran backbone. Initially, dextran was silylated with 1,1,1,3,3,3-hexamethyldisilazane. The grafting from pathway was conducted with various (30–70) PDO/OH feed ratios to obtain PODEX copolymers with a various PPDO graft structures. Graft copolymers were characterized by FT-IR, ¹H and ¹³C NMR, DSC, TGA, and WAXD. Molecular weights of the PODEX copolymers (M_W: 94,700–117, 300 Da), glass transition temperature (−29 to −17 °C), melting temperature (82–100 °C), and crystallinity (32–40%) were increased with the content of PPDO. AFM observations revealed that polymeric micelles were spherical and uniform in morphology with around 30–58 nm diameter. Critical micelle concentration (CMC) of self-assembled system was significantly decreased from 3.2 to 1.09 mg/L with the increment of PPDO.     

The role of phase separation and feed cycle length in leach beds coupled to methanogenic reactors for digestion of a solid substrate (Part 1): Optimisation of reactors' performance

A two-phase system composed by a leach bed and a methanogenic reactor was modified for the first time to improve volumetric substrate degradation and methane yields from a complex substrate (maize; Zeamays). The system, which was operated for consecutive feed cycles of different durations for 120 days, was highly flexible and its performance improved by altering operational conditions. Daily substrate degradation was higher the shorter the feed cycle, reaching 8.5 g TS_destroyed d⁻¹ (7-day feed cycle) but the overall substrate degradation was higher by up to 55% when longer feed cycles (14 and 28 days) were applied. The same occurred with volumetric methane yields, reaching 0.839 m³ (m³)⁻¹ d⁻¹. The system performed better than others on specific methane yields, reaching 0.434 m³ kg⁻¹ TS_added, in the 14-day and 28-day systems. The UASB and AF designs performed similarly as second stage reactors on methane yields, SCOD and VFA removal efficiencies.     

Synthesis and characterization of a brush-like copolymer of polylactide grafted onto chitosan

A brush-like poly(DL)-lactide grafted onto chitosan as the backbone was investigated. The graft copolymerization was carried out with triethylaluminum as catalyst in toluene at 70 degrees C. It was found that a greater lactide content in the feeding ratio results in a higher grafting percentage. FTIR spectrometry, (1)H NMR, DSC scanning, and wide-angle X-ray scattering, respectively, are used to characterize these branch copolymers. A copolymer has a definite melting point when the molar feeding ratio of lactide to chitosan is more than 10:1, and the deltaH of the copolymers increases with the feed ratio of lactide to chitosan in feeding.     

Graft copolymerization of ethylacrylate onto xanthan gum, using potassium peroxydisulfate as an initiator

Graft copolymer of xanthan gum (XG) and ethylacrylate (EA) has been synthesized by free radical polymerization using potassium peroxydisulfate (KPS) as an initiator in an air atmosphere. The grafting parameters, i.e. grafting ratio and efficiency decrease with increase in concentration of xanthan gum from 0.050 mg/25 mL to 0.350 mg/25 mL, but these grafting parameters increase with increase in concentration of ethylacrylate from 9 × 10⁻² to 17 × 10⁻² ML⁻¹, and KPS from 15 × 10⁻³ to 35 × 10⁻³ ML⁻¹. The graft copolymer has been characterized by FTIR, XRD, TGA and SEM analysis. The grafted copolymer was also evaluated as efficient Zn²⁺ metal binder. The grafted copolymer shows improvement in the stability, solubility as well as their sorbing capacity. Thus graft copolymer formed could find applications in metal ion removal and in drug delivery.     

Kinetics and mechanism of the reaction of octacarbonyl dicobalt with ethyl diazoacetate

Kinetics of the reaction of octacarbonyl dicobalt with ethyl diazoacetate leading to [μ²-{ethoxycarbonyl(methylene)}-μ²-(carbonyl)-bis(tricarbonyl-cobalt)] (Co-Co) (1), dinitrogen, and carbon monoxide were investigated at 10 °C in heptane solution. The initial rate of the reaction was measured by following both the gas evolution and the decrease of the octacarbonyl dicobalt concentration. The rate is first order with respect to octacarbonyl dicobalt and a complex order with respect to ethyl diazoacetate and carbon monoxide depending on the ratio of their concentrations. This is in accord with the formation of a heptacarbonyl dicobalt reactive intermediate (k₁ (10 °C) = (1.22 ± 0.06) × 10⁻³ s⁻¹) for which carbon monoxide and ethyl diazoacetate compete (k₋₁/k₂ (10 °C) = 1.34 ± 0.07).     

Amphiphilic and thermosensitive copolymers based on pullulan and Jeffamine: Synthesis, characterization and physicochemical properties

The synthesis of thermosensitive copolymers based on pullulan and polyether amine was performed in water using a water-soluble carbodiimide and N-hydroxysuccinimide as activators. Jeffamine^® M2005 was chosen as a polyether to impart thermosensitive character to the copolymer. Pullulan was modified into carboxymethylpullulan, to bring carboxylate groups to the polysaccharide so as to further the grafting reaction. The copolymers were characterized by FT-IR, ¹H NMR spectroscopy and molecular weights measurements (by SEC coupled with MALS/DRI/Viscometer lines). The thermosensitive behaviour of CMP-g-M2005 copolymers was studied by fluorescence spectroscopy of pyrene, by rheometry and microDSC measurements. The sol-gel transition temperature was found dependent on the solvent, the grafting degree of M2005 and the concentration of the copolymer. For example it was 35 °C in water, 28 °C in acid buffer (0.1 M, pH 5.4) and 26 °C in saline phosphate buffer (0.15 M, pH 7.4) for a grafting degree of 0.20 at a concentration of 5 wt%.     

Study of graft copolymerization of N-maleamic acid-chitosan and butyl acrylate by gamma-ray irradiation

N-maleamic acid-chitosan was synthesized and characterized by Fourier transform infrared spectra analysis (FT-IR) and 1H NMR. The graft copolymerization of N-maleamic acid-chitosan and butyl acrylate (BA) in acetic acid aqueous solution was investigated, using the gamma-ray of 60Co gamma-irradiation method. DSC (differential scanning calorimetry) trace of N-maleamic acid-chitosan-g-PBA has a glass-transition temperature (Tg) at -42 degrees C. The thermal stabilities of the graft copolymer were studied by the thermal gravimetric analysis (TGA). The effect of synthesis variables in the graft copolymerization have been discussed in the light of grafting efficiency, grafting percentage, and homopolymer percentage. Increasing grafting percentage was observed when the monomer concentration and total dose were increased or when the reaction temperature was decreased.     

Evaluation of the accessible inclusion sites in copolymer materials containing β-cyclodextrin

The accessible inclusion sites of insoluble copolymers containing β-cyclodextrin (β-CD) were studied in aqueous solutions by measuring the absorbance changes (decolourization) of phenolphthalein (phth) at pH 10.5. The various copolymers were reacted at different β-CD:crosslinker mole ratios with five individual types of crosslinker agents (epichlorohydrin (EP), sebacoyl chloride (SCL), terephthaloyl chloride (TCL), glutaraldehyde (GLU), and poly(acrylic) acid (PAA), respectively). The decolourization provided estimates of the 1:1 binding constants (K₁) for the β-CD monomer/phth complex. Comparable values of K₁ were measured for copolymer/phth complexes with highly accessible β-CD inclusion sites as compared with the 1:1 β-CD/phth complex. The surface accessibility of the β-CD inclusion binding sites for the polymers ranged from ∼10 to 72%. The observed variability of the inclusion sites was attributed to: (i) steric effects in the annular hydroxyl region of β-CD, (ii) the degree of crosslinking of the copolymer and (iii) the accessibility of the micropore sites within the copolymers. The Gibbs free energy (ΔG°) and site occupancy (θ) of phth adsorbed to the copolymer materials was estimated independently using the Sips isotherm model. The ΔG° values ranged between −27.6 and −30.9 kJ mol⁻¹ for the copolymers and are in close agreement with the value for the 1:1 β-CD/phth complexes (ΔG° = −27 kJ mol⁻¹) in aqueous solution.     

Comb-shaped graft copolymers with cellulose side-chains prepared via click chemistry

Comb-shaped copolymers with cellobiose acetate or cellulose triacetate (CTA) side-chains, PPMA-g-(CTA2-C15) and PPMA-g-(CTA13-C15), were prepared by grafting N-(15-azidopentadecanoyl)-2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-β-d-glucopyranosylamine (CTA2-C15-N₃) and N-(15-azidopentadecanoyl)-tri-O-acetyl-β-cellulosylamine (CTA13-C15-N₃, number average degree of polymerization (DP_n) = 13) onto poly(2-propyn-1-yl methacrylate) (PPMA, weight average degree of polymerization (DP_w, X + Y = 5.59 × 10²)) via “click chemistry”. The copolymers were characterized by ¹H, ¹³C and two-dimensional NMR and size exclusion chromatography-multi-angle laser light scattering (SEC-MALS) measurements. The numbers of CTA side-chains (X) of PPMA-g-(CTA2-C15) and PPMA-g-(CTA13-C15) were calculated as 4.03 × 10² and 2.45 × 10², respectively. Copolymers with cellulosic side-chains, PPMA-g-(CELL2-C15) and PPMA-g-(CELL13-C15), were successfully obtained after deacetylation of PPMA-g-(CTA2-C15) and PPMA-g-(CTA13-C15), respectively. X-ray diffraction measurements revealed that PPMA-g-(CELL13-C15) showed crystalline pattern of cellulose II, which is believed to have anti-parallel orientation.