A Study on Benzoylation and Graft Copolymerization of Lignocellulosic Cannabis indica Fiber

Present work deals with the surface modification of Cannabis indica fiber through benzoylation and graft copolymerization of acrylonitrile (AN) onto C. indica fibers under the influence of microwave radiations. The Benzoylation of C. indica fiber was carried out by treating raw fiber with varying concentrations of benzoyl chloride solution. Different reaction parameters for graft copolymerization, such as reaction time, initiator concentration, nitric acid concentration, pH and monomer concentration were optimized to get the maximum percentage of grafting (25.54%). A suitable mechanism to explain benzoylation and graft copolymerization has been also proposed. Raw C. indica fiber, graft copolymerized and benzoylated fibers were subjected to evaluation of some of their properties like swelling behavior, moisture absorbance and resistance towards chemicals. Cannabis indica fibers treated with 5% benzoyl chloride solution and AN graft copolymerized fibers have been found to show more resistant towards moisture, water and chemicals when compared with that of untreated fibers. Morphological, structural changes, thermal stability and crystallanity of raw, graft copolymerized and benzoylated fibers have also been studied by SEM, FTIR, TGA and XRD techniques. It has been observed that the crystallinity of fiber decreases but thermal stability increases on surface modification.     

Synthesis and Characterization of Chitosan-Grafted-Poly(2-Hydroxyaniline) Microstructures for Water Decontamination

Chitosan as a biopolymer, biodegradable, safe, non-toxic and widely abundant in nature was grafted with poly(2-hydroxyaniline) (P2-HA) through aqueous chemical oxidative copolymerization using ammonium persulphate in acetic acid medium. The grafting conditions were studied by varying grafting parameters. The effect of oxidant, 2-hydroxyaniline (2-HA) and acetic acid concentrations on the rate of copolymerization was studied. The synthesized graft characterized using UV–Vis, FTIR, TGA, XRD, and scanning electron microscope and compared with chitosan and P2-HA. The grafting enhances the thermal properties of chitosan. The effect of temperature on the rate of grafting copolymerization reaction was studied. The apparent activation energy (Ea) of the copolymerization reaction found to be 21.1116 kJ/mol. Also, ΔH^* and ΔS^*, were calculated and found to 22.8630 kJ/mol and ?109.4290 J/mol K respectively. The mechanism of the grafting copolymerization reaction discussed. Chitosan, P2-HA and chitosan-graft-P2-HA used for the removal of Cr, Fe, Mn, Cu and Zn divalent ions from a contaminated water samples. The adsorption isotherm parameters are given.     

Synthesis and identification of graft copolymers of wood pulp and styrene

Based on the graft copolymerization reactions of lignin and vinyl monomers, a series of graft copolymers of wood pulp and styrene (1-phenylethene) has been synthesized. The wood pulps used in this research are unbleached products produced by chemical, thermal, and mechanical pulping. All of them contain a high content of lignin (25–29 wt%). The grafting reaction is a free radical polymerization coinitiated by calcium chloride, hydrogen peroxide, and wood pulp in dimethylsulfoxide at 30°C. The effect of reaction temperature, reaction time, and the amount of the reactants on the conversion of monomer, yield of product, weight increase of pulp, and grafting efficiency of monomer has been studied. The grafted wood pulp was separated from homopolystyrene formed during the reaction by extraction of the reaction product with benzene in a Soxhlet apparatus for at least 48 h. The results show that after the reaction, the weight of all wood pulps was significantly increased and the weight increase of very high yield sodium bisulfite pulp (VHYS) was 333%. This proves that a part of the polymerized styrene was chemically bound to the wood pulp. The Fourier transform infrared (FTIR) spectra of the extracted products show absorbance peaks characteristic of both wood and polystyrene and, thus, provide strong proof of grafting. Grafting has completely changed the surface properties of the starting wood pulp from hydrophilic to hydrophobic, and under ordinary thermal compression conditions, thermoplastic composite objects of good uniformity can be made directly from reaction products which contain up to 52 wt% wood pulp.     

Novel Environmentally Friendly Copolymers Carboxymethyl Starch Grafted Poly(Lactic Acid)

Modified natural polymers have been gaining increasing scientific interest for many years. In this study carboxymethyl starch (CMS) was grafted with L(+)-lactic acid (LA) in different molar ratios CMS/LA (1/36, 1/22 and 1/12), resulting carboxymethyl starch-g-poly(lactic acid) (CMS-g-PLA) copolymers. The grafting reaction was carried out by solution polycondensation procedure in toluene and stannous 2-ethyl hexanoate Sn(Oct)₂ as catalyst was utilized. Poly(lactic acid) (PLA) was synthesized in the same conditions with the copolymers for comparative analyses of the physico-chemical and thermal properties. The copolymers and PLA were structurally and morphologically characterized by FT-IR, ¹H-NMR spectroscopy, WAXD and SEM analyses, taking CMS as reference. The molecular weight of the copolymers, CMS and PLA were determined, using a dynamic light scattering technique. The thermal behavior of the products was studied by DSC and TG-DTG analyses. The CMS-g-PLA graft copolymers exhibited lower Tg and thermal stability than pure CMS.     

Comparison of Cationic and Unmodified Starches in Reactive Extrusion of Starch–Polyacrylamide Graft Copolymers

Graft copolymers of starch and polyacrylamide (PAAm) were prepared using reactive extrusion in a corotating twin screw extruder. The effect of cationic starch modification was examined using unmodified and cationic dent starch (≈23% amylose) and waxy maize starch (≈2% amylose). For a fixed acrylamide/starch feed ratio, conversion, graft content, and grafting efficiency were essentially unaffected by starch type or modification. Cationic starch graft copolymers generally had lower molecular weight PAAm grafts compared to the unmodified starch, whereas amylose content had little or no significant effect. In addition, the frequency of grafting was higher with cationic starch. These results indicate that cationic modification of starch enhances formation of grafting sites, resulting in graft copolymers with more grafts of lower molecular compared to unmodified starch. Cationic modification may therefore be a way to tailor the properties of starch–PAAm graft copolymers.     

Itaconic Acid Grafted Starch Hydrogels as Metal Remover: Capacity,Selectivity and Adsorption Kinetics

Hydrogels were synthesized by free radical graft copolymerization of itaconic acid (IA) onto corn starch (S-g-IA). For this purpose, potassium permanganate (KMnO₄)-sodium bisulfite (NaHSO₃) was used as redox initiation system. The formation of grafted starches was confirmed by Fourier transform infrared spectroscopy, wide angle X-ray scattering, thermogravimetric analysis and scanning electron microscopy. The effect of monomer concentration, neutralization, addition of crosslinking agent, N,N-bismetilenacrilamide (MBAm), and initiator concentration on grafting efficiency and adsorption capacity of the starch hydrogels was investigated. It was demonstrated that the introduction of carboxyl and carbonyl groups promoted starch hydration and swelling. Grafting degree increased with the decrease of monomer concentration, increase of initiator concentration, grade of neutralization and the addition of MBAm without neutralization. Remarkably the resulting materials exhibited water absorption capacities between 258 and 1878% and the ability to adsorb metal ions. It was experimentally confirmed the metal uptake, obtaining the higher adsorption capacity (q _e  = 35 mg/g) for the product prepared with the pre-oxidation and lower initiator concentration. The removal capacity order was Pb²⁺>Ni²⁺>Zn²⁺>Cd²⁺. Moreover, the experimental kinetic and the equilibrium adsorption data for Ni²⁺ and Pb²⁺ were best fitted to the pseudo-second order and Freundlich isotherm models, respectively. This work describes for the first time the preparation of metal removal hydrogels based on starch and itaconic acid using the pair redox system KMnO₄/NaHSO₃, which avoids the starch hydrolysis and allows itaconic acid grafting incorporation without the requirement of more reactive comonomers.     

Photo-/Bio-degradability of Agro Waste and Ethylene–Propylene Copolymers Composites Under Abiotic and Biotic Environments

Composites were prepared by two methods, (i) graft copolymerization (GFC) of isotactic polypropylene (PP) with maliec anhydride, (MAH) followed by esterification with coir fiber and (ii) by direct reactive mixing (DFC) of polypropylene (PP) and ethylene–propylene (EP) copolymers with MAH and peroxide with coir fiber. These composites, after molding in films (5×5 cm, m thickness) were examined for susceptibility to biological attack by measuring the percentage weight loss in compost upto 6 months, periodically, and fungal colonization on surface of the samples, when kept as sole carbon source for the growth of Aspergillus niger in culture medium upto 40 days. Photodegradation was evaluated by monitoring the variations in FT-IR spectrum and crack formation after successive treatment with UV light (≥290 nm) for 0, 20, 50 and 100 h at 60°C in the presence of air. Specimens of virgin PP were taken as a reference during all period of photo and biodegradation studies. Significant changes were observed depending on the preparation methods during photodegradation and biodisintegration of composites. DFCs samples were disintegrated faster than GFCs during the composting whereas, in culture, GFCs were covered highly in well uniform way by fungi. It was observed that photo-oxidative ageing directly enhanced the biodegradability of composites as the increase in fungal growth rate and decrease in weight during composting were found. It was concluded that extent of compatibilization had a profound effect on photo-oxidation and biodisintegration of composite material; consequently ester bonds were main units during fungal consumption. Composition of monomers in copolymers was also showing significant effect on the degradability which decreased with increasing content of ethylene in ethylene–propylene (EP) copolymers.     

Reactive Extrusion of Starch–Polyacrylamide Graft Copolymers Using Various Starches

Graft copolymers of polyacrylamide and various substrates were prepared by reactive extrusion in a twin screw extruder using ammonium persulfate as initiator. Substrates included unmodified starches (corn, waxy maize, wheat, and potato), cationic starches, dextrin, dextran, and polyvinyl alcohol (PVOH). The feed ratio of substrate to monomer was 2:1. Average conversion of monomer to polymer was 88.9% (±5.1%). Graft contents for the starch substrates were approximately 25% with grafting efficiencies of about 70%. Polyacrylamide graft molecular weights ranged from 317,000 to 769,000. Absorbencies at pH 7 for saponified graft copolymers prepared with unmodified starches were approximately 200 g/g and approximately 150 g/g for the cationic starches, dextran, and PVOH. In electrolyte solution (0.9% NaCl), absorbencies were in the range of 26–59 g/g, depending on substrate type. Saponified dextrin copolymers were essentially soluble with absorbencies of 6 g/g in water and 12 g/g in 0.9% NaCl.Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Investigation of Synthesis of Copolymers from the Waste Products of Industrial Oil Refinement having Adhesion Properties and Strength to the Thermal Destruction

In this study, the waste products of industrial vegetable oil refinement were transformed into the glycidyl ester for preventing the effects of them to the environment, the ways for evaluating them in polymer chemistry were investigated, copolymers having high adhesion property and strength to the thermal destruction were synthesized and the area of their usage was determined. For this reason, the waste product of sunflower oil refination as a vegetable oil in the industry; soap stock (SS) was converted to the unsaturated glycidyl esters by the interaction with epichlorohidrine in the alkaline medium. After that the copolymerization of synthesized unsaturated glycidyl esters and the other waste product of oil refinement fatty acid (FA) with styrene in the radicalic initiator medium were investigated and copolymers that have high strength to the thermal destruction and adhesion property were synthesized. From the results of TGA and DTA analysis, it was determined that synthesized copolymers have low loss of weight at high temperature. The structures of copolymers were fixed by spectral and chemical analysis methods.     

Surface Modification of Sisal Fibers (Agave sisalana) Using Bacterial Cellulase and Methyl Methacrylate

The hydrophilic nature of cellulose fibers often results in poor compatibility with hydrophobic polymer matrices. Therefore, it becomes necessary to modify the surface of natural fiber for better binding between fiber and matrix. Chemicals are commonly used for the modification of cellulosic materials but large amount of solvents are usually involved. Microwave radiation induced grafting is one of the promising methods for the surface modification of natural fibers. In the present paper, we have reported the microwave radiations induced grafting onto sisal fibers (Agave sisalana) using methyl methacrylate monomer, which has been compared to the surface modification of sisal fibers using bacterial cellulase. The effects of these treatments on the properties of sisal fibers are discussed in the present paper. The modified fibers were characterized by scanning electron microscopy, X-ray diffraction, and thermogravimetric analysis/differential thermal analysis techniques to determine their morphology, crystallinity and thermal stability.     

Synthesis of Short-chain-length/Medium-chain-length Polyhydroxyalkanoate (PHA) Copolymers in Peroxisome of the Transgenic Arabidopsis Thaliana Harboring the PHA Synthase Gene from Pseudomonas sp. 61-3

In this paper, the photosynthetic production of short-chain-length/medium-chain-length polyhydroxyalkanoate (PHA) copolymers is reported. The wild-type and highly active doubly mutated PHA synthase 1 (S325T/Q481K, abbreviated ST/QK) genes from Pseudomonas sp. 61-3 were introduced into Arabidopsis thaliana. Peroxisome targeting signal 1 (PTS1) was used to target PHA synthases into the peroxisome to synthesize PHA from the intermediates of the β-oxidation pathway. The transgenic Arabidopsis produced PHA copolymers consisting of 40–57 mol% 3-hydroxybutyrate, 21–49 mol% 3-hydroxyvalerate, 8–18 mol% 3-hydroxyhexanoate, and 2–8 mol% 3-hydroxyoctanoate. The maximum PHA contents were 220μ g/g cell dry weight (cdw) in leaves, and 36μ g/g cdw in stems, respectively. The expression of the ST/QK mutated PHA synthase in leaves gene did not lead to significant difference in PHA content and monomer composition of PHAs, compared to the wild-type PHA synthase gene, suggesting that the supply of monomers may be a rate-determining step of PHA biosynthesis in the peroxisome. However, in stems, there were significant differences dependent on whether the wild-type or ST/QK mutated PHA synthase was expressed. These results suggest that tissue-specific monomer availability is important in determining the final mol% composition of PHA copolymers produced by the peroxisome in plants.     

Studies on the enzymatic and fungal degradation of cross-linked gelatin and its graft copolymers

Glutaraldehyde cross-linked gelatin was graft copolymerized with acrylic acid, acrylamide, vinyl acetate, methyl acrylate, and methyl methacrylate either individually or in combination. The enzymatic and fungal degradation of these graft copolymers with trypsin, pepsin, and mixed cultures ofAspergillus niger, Penicillium ochrochloron, Penicillium funiculosum, andTrichoderma viride was studied for short and extended periods. The weight loss suffered by the samples, the weight of biomass formed, the nitrogen content, and the pH of the culture medium were determined. With the help of these data, the extent of utilization of graft copolymers by fungi as a sole source of carbon was estimated. The samples with less than 100% grafting and with a ratio of polymethyl methacrylate content (L) to polyacrylic acid (H) content (L/H values) lower than 1.0 were readily and extensively degraded.IICT Communication No. 3375.     

Green Synthesis and Physical Properties of poly(Vinyl Alcohol) Maleated in an Aqueous Solutions

The objective of this work was to synthesize maleated poly(vinyl alcohol) (PVAM) in aqueous solution through esterification, and to seek near optimal degree of grafting and crosslinking. The effects of maleic anhydride (MA) content on the properties of PVAM were investigated. The experimental observations included characterizations by ATR–FTIR and thermo gravimetric analyses (TGA), and determinations of grafting ratio, dynamic viscosity, and swelling ratio. The percentage degree of grafting, dynamic viscosity, and particle size increased with MA content, while the swelling ratio decreased due to copolymerization of poly(vinyl alcohol) (PVA) and MA. The peaks at 945 and 918 cm^?1 in the spectrum of PVA indicated the presence of carboxylic groups, while in the spectrum of PVAM only one peak at 920 cm^?1 indicated presence of carboxylic groups, due to copolymerization of PVA and MA. Moreover, the thermal stability of PVA-g-MA was enhanced as observed from TGA. The results suggest 7:3 PVA/MA mass ratio as near optimal for PVA-g-MA.     

A Critical Review on Natural Fibers Modifications by Graft Copolymerization for Wastewater Treatment

Graft copolymerization is a distinctive approach to modify the inherently cheap natural fibers (NFs) using different initiators to incorporate synthetic polymer side chains allowing development of novel types of hybrid materials. This method has been widely applied to develop a variety of NFs based adsorbents for decontamination of toxic pollutants from the aqueous environment. However, the development of high-performance adsorbents from NFs is steady challenged by the need to preserve the sustainability during graft modifications and applications. This article critically reviews the progress on modifications of NFs by graft copolymerization of polar monomers on NFs using various initiating methods and their applications in wastewater treatment. Particularly, the applications of the grafted NFs in removal of heavy metal ions, synthetic dyes, oil spills and extraction of precious metals from wastewater are elaborated. The critical challenges to the viability and sustainability of NFs-based adsorbents with respect to functionalization by graft copolymerization and environmental impacts are discussed and the future research directions are also outlined.

     

Different Pla Grafting Techniques on Chitosan

PLA grafting on chitosan has been successfully prepared with two different methods: a direct grafting method and the ROP method. The thermal properties showed that the copolymerization of PLA on the chitosan’s chain by direct grafting is more thermostable than the one obtained by the ROP method.     

Effect of Decalin Solvent on the Thermal Degradation of HDPE

The thermal cracking of HDPE in presence of different amounts of decalin was studied and compared with the reaction carried out in the absence of solvent. The decalin favours the mass and heat transfer during the reaction. In addition, it modifies the thermal degradation mechanism, which facilitates the formation of specific products. The use of decalin substantially increases the C₅–C₃₂ yield in comparison with the solventless reaction. In all cases, linear hydrocarbons such as n-paraffins, α-olefins and α,ω-dienes were detected. Increasing the decalin/plastic ratio led to enhanced α-olefin and n-paraffins yields, but the increase was more significant in the case of α-olefins, which are valuable compounds useful as raw chemicals. A reaction mechanism was proposed to explain the results obtained in presence of decalin. In these reactions, intramolecular radical transfer, secondary radical β-scission and hydrogen transfer from both decalin to intermediate radicals and from the polymer chain to regenerate the decalin play a significant role in determining the plastic conversion and the relative amounts of each product.     

Selective Lead(II) Adsorption and Flocculation Characteristics of the Grafted Sodium Alginate: A Comparative Study

Synthesis of sodium alginate-g-poly(acrylamide-co-N-methylacrylamide) [S-III], sodium alginate-g-poly(N-methylacrylamide-co-N,N-dimethylacrylamide) [S-II], sodium alginate-g-poly(acrylamide-co-N,N-dimethylacrylamide) [S-I]. Sodium alginate-g-poly(N,N-dimethylacrylamide) [SAG-g-PDMA] and sodium alginate-g-poly(acrylamide) [SAG-g-PAM] were prepared by solution polymerization technique using potassium peroxydisulfate as the initiator at 70?°C in water medium. The graft copolymers were characterized by FTIR and NMR (¹H and ¹³C) spectroscopy, SEM and XRD studies. All the five graft copolymers were used to remove Pb(II) ions from the aqueous solution and also in flocculation studies of kaolin clay (1.0 wt%), silica (1.0 wt%) and iron ore slime (0.25 wt%) suspensions. A comparative studies of all the five graft copolymers were also made in both the two cases. The Pb(II) ion removal capacity of all the graft copolymers follows the order S-III?>?SAG-g-PAM?>?S-II?>?SAG-g-PDMA?>?S-I. But the flocculation performance of the graft copolymers follows the order S-II?>?S-I?>?S-III?>?SAG-g-PDMA?>?SAG-g-PAM. S-III was also used for the competitive metal ion removal with Hg(II), Cd(II), Cu(II) and Zn(II). Pb(II) adsorption of S-III (the best Pb(II) ion adsorber) follows pseudo second order rate equation and Langmuir adsorption isotherm.     

Syntheses of Biodegradable Functional Polymers by Radical Ring-Opening Polymerization of 2-Methylene-1,3,6-trioxocane

2-Methylene-1,3,6-trioxocane (MTC) was polymerized via ring-opening in the presence of a radical initiator and the obtained polyester was biodegradable. MTC could also copolymerize with various vinyl monomers such as styrene, vinyl acetate, methyl vinyl ketone, N-vinyl-2-pyrrolidone, N-isopropyl acrylamide, and maleic anhydride. By copolymerizing MTC with these vinyl monomers in the presence of a radical initiator, we could obtain various biodegradable polymers with ester group introduced into the backbone. In addition the obtained copolymers exhibit certain functionalities such as photolysis, water-solubility, thermosensitivity, detergent builder, and water-absorbability.     

The Synthesis and FTIR, Kinetics and TG/DTG/DTA Study of Inter Penetrating Polymer Networks (IPNs) Derived from Polyurethanes of Glycerol Modified Castor Oil and Cardanol Based Dyes

Interpenetrating polymer networks from agricultural products such as glycerol modified castor oil polyurethanes and cardanol based dyes have not been extensively studied so far. Such polymers were synthesized using benzoyl peroxide as initiator and ethylene glycol dimethacrylate as cross-linker. Characterizations of these polymers were performed by Fourier Transform infra red spectra and thermal analysis techniques such as thermogravimetric analysis, derivative thermogravimetry and differential thermal analysis. The kinetic parameters such as activation energies and orders of reaction were estimated by using Freeman?CAnderson??s method. The effects of changes in polyurethane to dye monomer weight ratio and NCO/OH molar ratio of polyurethanes on the properties of such polymers were studied.