Biodegradation of gelatin graft copolymers. III

Gelatin-g-poly(methyl acrylate) and gelatin-g-poly(acrylonitrile) copolymers were prepared in an aqueous medium using K₂S₂O₈ initiator. A plausible mechanism has been put forward for the observed grafting behavior of monomers. Gelatin-g-PAN showed a greater resistance to mixed bacterial inolucum compared to gelatin-g-PMA samples. The rate of degradation decreased with the increase in grafting efficiency. A parallel set of experiments carried out by employing the samples as the only source of both carbon and nitrogen showed a marginal but definite increase in the utilization of the polymer. The nitrogen analysis also showed the utilization of the polymer. Scanning electron micographs of the polymer films do show extensive pitting after microbiological testing.     

Biodegradation of gelating-g-poly(ethyl acrylate) copolymers. II

Gelatin-g-poly(ethyl acrylate) copolymers were prepared in an aqueous medium using K₂S₂O₈ initiator. Three copolymer samples with grafting efficiencies of 33.3%, 61.0%, and 84.0% were tested for their microbial susceptibility in a synthetic medium with pure cultures of Pseudomonas aeruginosa, Bacillus subtilis, and Serratia marcescens. The percent weight losses were recorded over 6 weeks of incubation period in nitrogen-free and nitrogen-rich media. The relationship between [log (rate)] during the first week of the test period and the composition of grafted samples showed a linear behavior. Pure cultures were more effective than the mixed inoculum, although there was no essential difference in the agressivity of different bacterial stains. Growth–time curves and pH measurement also complement these observations.     

Graft copolymerization of vinyl monomers on cellulosic materials

Graft copolymers of acrylonitrile, ethyl acrylate, methyl acrylate, ethyl methacrylate and methyl methacrylate and of acrylonitrile/ethyl methacrylate and acrylonitrile/methyl methacrylate monomer mixtures on carboxymethylcellulose (degree of substitution 0.4–0.5) were prepared by use of ceric ion initiator in aqueous medium. The extent of graft polymer formation was measured in terms of graft level, molecular weight of grafted polymer chains and frequency of grafting as function of ceric ion concentration. It was found that at comparable reaction conditions, the molecular weight and frequency of grafting were not of the same order of magnitude. For the monomer mixtures, the copolymer compositions obtained from the total nitrogen content of the acrylonitrile/alkyl methacrylate copolymer samples showed that a relativity low amount of the acrylonitrile monomeric units were incorporated into the graft copolymer even at high acrylonitrile content of the feed.     

Study of thermal and dyeing behavior of isotactic polypropylene fiber graft copolymerized with acrylate monomers using preirradiation method

In an attempt to modify isotactic polypropylene (IPP) fiber, grafting of acrylate monomers such as methyl acrylate (MA) and ethyl acrylate (EA) onto IPP has been carried out by preirradiation method in aqueous medium. Percentage of grafting has been determined as a function of various reaction parameters. Rate of grafting (R_g) and induction period (I_p) have been evaluated as a function of total initial monomer concentration. Methyl acrylate was found to be more reactive than ethyl acrylate toward grafting. Thermogravimetric analysis (TGA) indicates that the thermal stability of polypropylene fiber is significantly improved upon grafting. While polypropylene fiber could not be dyed by crystal violet, the grafted fiber was dyed with crystal violet, and the dye uptake has been quantitatively determined by spectrometric method. © 1994 John Wiley & Sons, Inc.     

Preparation,characterization, and properties of cellulose–polyacrylamide graft copolymers

Graft copolymers of acrylamide on cellulose materials (α‐cellulose 55.8%, DP 287.3) obtained from Terminalia superba wood meal and its carboxymethylated derivative (DS 0.438) were prepared using a ceric ion initiator and batch polymerization and modified batch polymerization processes. The extent of graft polymer formation was measured in graft level, grafting efficiency, molecular weight of grafted polymer chains, frequency of grafting as a function of the polymerization medium, and initiator and monomer concentrations. It was found that the modified batch polymerization process yielded greater graft polymer formation and that graft copolymerization in aqueous alcohol medium resulted in enhanced levels of grafting and formation of many short grafted polymer chains. Viscosity measurements in aqueous solutions of carboxymethyl cellulose‐g‐polyacrylamide copolymer samples showed that interpositioning of polyacrylamide chains markedly increased the specific viscosity and resistance to biodegradation of the graft copolymers. The flocculation characteristics of the graft copolymers were determined with kaolin suspension. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 913–923, 2003     

Preparation and characterization of polyaniline N‐grafted with poly(ethyl acrylate) synthesized via atom transfer radical polymerization

Polyaniline (PANI) N‐grafted with poly(ethyl acrylate) (PEA) was synthesized by the grafting of bromo‐terminated poly (ethyl acrylate) (PEA‐Br) onto the leucoemeraldine form of PANI. PEA‐Br was synthesized by the atom transfer radical polymerization of ethyl acrylate in the presence of methyl‐2‐bromopropionate and copper(I) chloride/bipyridine as the initiator and catalyst systems, respectively. The leucoemeraldine form of PANI was deprotonated by butyl lithium and then reacted with PEA‐Br to prepare PEA‐g‐PANI graft copolymers containing different amounts of PEA via an N‐grafting reaction. The graft copolymers were characterized by Fourier transform infrared spectroscopy, elemental analysis, and thermogravimetric analysis. Solubility testing showed that the solubility of PANI in chloroform was increased by the grafting of PEA onto PANI. The morphology of the PEA‐g‐PANI graft copolymer films was observed by scanning electron microscopy to be homogeneous. The electrical conductivity of the graft copolymers was measured by the four‐probe method. The results show that the conductivity of the PANI decreased significantly with increasing grafting density of PEA onto the PANI backbone up to 7 wt % and then remained almost constant with further increases in the grafting percentage of PEA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Aminolysis reaction of poly(N-4-methylphenylitaconimide) and its graft copolymerization

Polyitaconimide and copolymers of itaconimide were transformed to macromolecules having diamido pendent groups via an aminolysis reaction. The polymers obtained were cast into films, which were then graft copolymerized with acrylamide (AAM) using ceric ion as an initiator. Radical homopolymerization and copolymerization of N-4-methylphenylitaconimide with methyl acrylate or ethyl acrylate were carried out at 60°C in benzene; high molecular weight polymer and copolymers (M?_n = 10⁴–10⁵) were obtained. The resulting polymer and copolymers were reacted with n-butylamine in order to produce polymers possessing a pendent 4-tolylcarbamoyl group (4-CH₃C₆H₄NHCO-), which can significantly promote the acrylamide (AAM) graft copolymerization initiated with ceric ion. Transparent films of the polymers were graft copolymerized with AAM in the presence of ceric ion at 45°C. The formation of graft polymers was verified by water absorption percentage, XPS and SEM.     

Copolymerization of pentachlorophenyl acrylate with vinyl acetate and ethyl acrylate. Polymer-bound fungicides

Copolymers of pentachlorophenyl acrylate (M₁) with both vinyl acetate and ethyl acrylate were prepared (in benzene at 60°C initiated by t-butyl peroxypivalate) at a variety of M₁/M₂ ratios. The reactivity ratios for the vinyl acetate (M₂) copolymerizations were r₁ = 1.44 and r₂ = 0.039, while for ethyl acrylate copolymerizations r₁ = 0.21 and r₂ = 0.88. The glass transition temperatures were obtained as a function of the M₁/M₂ ratio. The values of T_g for the copolymers fell between those of poly(pentachlorophenyl acrylate) and either poly(vinyl acetate) or poly(ethyl acrylate). A series of bulk copolymers with low pentachlorophenyl acrylate content were studied as biocidal coatings using accelerated growth agar dish tests inoculated with Aspergillus sp., Pseudomonas sp., Alternaria sp., and Aureobasidium pullulans. The copolymers retarded or prevented growth but did not give a zone of inhibition around the coatings. Pentachlorophenol, when added to coating polymers, did exhibit a zone of inhibition due to migration of this biocide into the agar medium.     

Functional nano-fillers in waterborne polyurethane/acrylic composites and the thermal,mechanical, and dielectrical properties

Modification is mostly used to adjust and increase the performance of polymers by employing organic or inorganic fillers in composites. It is significant to investigate the functions of different fillers in polymer matrix. In this work, we prepared a series of composites by using polyurethane/acrylic dispersions as polymer matrix and nanofillers (cellulose nanocrystals, carbon nanotubes and aluminum oxide nanoparticles) as modifiers to study their micro-structure and applied performance. It is found that the different nanofillers can be dispersed in PUA homogenously, which are inclusive physically. Different nanofillers have a noticeable influence on the T_g for the acrylate copolymers and the T_g of the interphase between the acrylate and polyurethane. The CNTs significantly increases the elongation to 127.29%, and gives the highest dielectric response. We imply that the CNTs may be the most significant fillers to increase the mechanical and electrical properties.     

Resultant synergism in the shear resistance of acrylic pressure‐sensitive adhesives prepared by emulsion polymerization of n‐butyl acrylate/2‐ethyl hexyl acrylate/acrylic acid

Acrylic emulsion pressure‐sensitive adhesives (PSAs) were synthesized by the copolymerization of n‐butyl acrylate with various levels of 2‐ethyl hexyl acrylate (2EHA) and a small constant amount of acrylic acid. The effect of varying the n‐butyl acrylate/2EHA monomer composition on the kinetic behavior of the polymerization and the characteristics of the copolymers prepared in a batch process were investigated. The results showed that increasing the amount of 2EHA in the monomer caused the polymerization rate and the glass‐transition temperature of the acrylic copolymers to decrease. Increasing the amount of 2EHA caused the gel content of the copolymers to decrease, reaching a minimum at 50 wt %; thereafter, the gel content increased at higher 2EHA levels. For the acrylic emulsion, the peel‐fracture energy of the PSAs decreased as the amount of 2EHA in the monomer was increased up to 50 wt %. At higher 2EHA levels, the peel‐fracture energy was relatively constant. Interestingly, a synergistic effect of increased shear resistance at 25 wt % 2EHA was observed without a significant trade‐off in terms of the peel and tack properties. This behavior was attributed to a good interconnection between the microgels and the free polymer chains inside the contacting particles in the adhesive film. Cooperation between various levels of 2EHA in the copolymer structure simultaneously changed the crosslink molecular weight (M_c) of the microgels and the entanglement molecular weight (M_e) of the free chains in the adhesive network morphology. The adhesive performance of the PSAs was found to be correlated with their M_c/M_e values as the 2EHA proportion was varied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Terpolymers. I. The mechanical properties and transition temperatures of terpolymers of n-octadecyl acrylate,ethyl acrylate,and acrylonitrile

Earlier work revealed that the internal plasticization of polyacrylonitrile by the higher n-alkyl acrylates or N-n-alkylacrylamides yielded only brittle copolymers. This difficulty was circumvented in the present work by starting with copolymers of acrylonitrile and ethyl acrylate, over the range of compositions, and further modifying these by incrementally displacing the ethyl acrylate in each recipe by n-octadecyl acrylate through terpolymerization. In this way, the stepwise small reduction in T_g for the base ethyl acrylate–acrylonitrile copolymers was greatly increased for each of the terpolymers. Compositions were obtained ranging from glassy, brittle terpolymers, with glass transitions above room temperature, to soft plasticized polymers having sufficient polar networks retained from the nitrile to confer useful properties. The decline in the glass temperature was shown to be dependent on the free volume conferred by the side-chain methylene groups of each acrylate ester. In contrast, the decline in tensile and flexural strengths and moduli for the terpolymers having glass transitions above room temperature was produced entirely by the presence of the methylene groups of the 18-carbon ester. The glass transition region corresponded to room temperature when the acrylonitrile content of the base copolymer had been reduced to 50 mole-%. Terpolymers of this nitrile content and lower had the low moduli and large elongations of plasticized compositions. An equation was developed which correlated empirically the glass transitions and the mechanical properties with the weight fraction of the acrylate esters for the glassy terpolymers.     

Synthesis of chitosan‐graft‐poly[2‐cyano‐1‐(pyridin‐3‐yl)allyl acrylate] copolymer from a novel monomer,prepared using a Morita–Baylis–Hillman reaction,and characterization of its antimicrobial activity

A novel method has been developed to modify the natural polymer chitosan. The process utilizes a monomer prepared by employing a Morita–Baylis–Hillman (MBH) reaction. Specifically, the vinyl monomer 2‐[hydroxy(pyridin‐3‐yl)methyl]acrylonitrile (HPA) was synthesized using a high‐yielding MBH reaction of acrylonitrile with pyridine‐3‐carboxaldehyde in the presence of 1,4‐diazabicyclo[2.2.2]octane. Conversion of HPA to 2‐cyano‐1‐(pyridin‐3‐yl)allyl acrylate (CPA) was then carried out by reaction of acryloyl chloride. The highly functionalized monomer CPA was grafted onto chitosan through a reaction in 2% acetic acid containing a persulfate and a sulfite (K₂S₂O₈/Na₂SO₃) as redox promoter. An optimal grafting percentage of 123% is obtained when the grafting process is conducted at 60 °C for 4 h employing a 1:0.5 ratio of K₂S₂O₈ and Na₂SO₃ at a concentration of 2.5 × 10^?3 mol L^?1. Chitosan‐graft‐poly[2‐cyano‐1‐(pyridin‐3‐yl)allyl acrylate] graft copolymers, having various grafting percentages, were characterized using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopies, X‐ray diffraction, thermogravimetric analysis and scanning electron microscopy. Finally, the results of studies probing the antimicrobial activities of the polymers against selected microorganisms show that the graft copolymers display higher growth inhibition activities against bacteria and fungi than does chitosan. © 2014 Society of Chemical Industry     

Grafting of ethyl acrylate onto gelatin in water-isopropanol medium

Graft copolymers were synthesized by grafting ethyl acrylate onto gelatin. The reaction was carried out in water-isopropanol medium (1:1 v/v). Reactions take place within 90 min. The resulting product is insoluble in solvents for the respective homopolymers. Presence of vinyl polymer was confirmed by IR spectra.     

Carbon black‐filled poly(ethylene‐co‐alkyl acrylate) composites: Calorimetric studies

The calorimetric characteristics of carbon black (CB)/poly(ethylene‐co‐alkyl acrylate) composites depend on both the CB and acrylate contents. An increase of the acrylate content in the pure copolymers tends to decrease all the crystalline characteristics: T_c,n, the nonisothermal crystallization temperature; T_m, the melting temperature, and ΔH_m, the melting enthalpy. CB modifies the crystallization kinetics of poly(ethylene‐co‐ethyl acrylate) (EEA) alone and in blends with poly(ethylene‐co‐24% w/w methyl acrylate) (24EMA) and poly(ethylene‐co‐35% w/w methyl acrylate) (35EMA). In the presence of CB, T_c,n, the nonisothermal crystallization temperature of EEA, increases and t_1/2, the half‐crystallization time, decreases for a given isothermal crystallization temperature, T_c,i. The thermograms obtained during the melting of EEA after isothermal crystallization show multiple endotherms, suggesting that crystalline‐phase segregation has occurred. The existence of different crystalline species can be explained by the presence of fractions of different acrylate content in the copolymers as shown by SEC. Therefore, CB does not seem to have much effect on the subsequent melting temperature of EEA, T_m,s. CB also induces a lower melting enthalpy, Δ H_m, in the blends. This decrease of ΔH_m appears to be constant whatever the compound, but when reported to the melting enthalpy of the polymer without CB, δΔH_m/ΔH_m increases with the acrylate content. A slight increase of the amorphous phase stiffness after CB introduction is noticed: The T_g of EEA/24EMA and EEA/35EMA blends increases by several degrees. Therefore, plotting ΔH_m versus ΔC_p shows that for the same ΔH_m the ΔC_p is lower in CB‐filled samples, suggesting there is some kind of rigid amorphous phase not contributing to the glass transition. We propose to explain the CB activity during the crystallization process by the existence of molecular interactions between CB and acrylate groups rather than by a pure nucleating effect. Thus, the increase of T_c,n and the decrease of ΔH_m could be explained by the fact that CB separates acrylate‐rich chains from the crystallization medium, accelerating the crystallization of the acrylate‐poor chains. During such a crystallization process, CB may be preferentially localized in the more polar amorphous phase and scattered between the two crystalline phases of EEA and EXA. These blends of poly(ethylene‐co‐alkyl acrylate) copolymers with CB provide interesting materials with adjustable properties depending on the acrylate and CB contents and on the thermomechanical treatments. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 779–793, 2001     

Thermal behavior of graft copolymers of cotton cellulose and acrylate monomers

Cotton cellulose yarn was grafted with methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate at various percentages of grafting. The effects of concentration of the initiator, concentration of the acid, and of temperature on grafting was studied and the mechanism discussed. The effect of reactivity of the monomer on the percentage graft-on is pointed out. Thermal behavior of natural and grafted cotton yarn was studied using dynamic thermogravimetry in air at a heating rate of 6°C/min up to a temperature of 500°C. The thermal stabilities of the samples grafted with various acrylate monomers to various percentages of grafting were computed from their primary thermograms by calculating the values of IDT, IPDT, and E^*. The results show that the thermal stability increases with increase in graft-on per cent, and the thermal stabilities of natural cotton and cotton grafted with different monomers are in the order ethyl > methyl > natural cellulose > methyl methacrylate > n-butyl acrylate.     

Graft copolymerization of starch with methyl acrylate: An examination of reaction variables

Starch-g-poly(methyl acrylate) (S-g-PMA) copolymers containing 55–60% PMA were prepared from cornstarch, high amylose cornstarch, and waxy cornstarch with ceric ammonium nitrate initiation. Graft copolymers were characterized with respect to % PMA homopolymer, % conversion of monomer to polymer, grafted PMA content, grafting frequency, and the molecular weight and molecular weight distributions of PMA grafts. Variables investigated in the graft copolymerization reaction were nitric acid concentration, ceric ion-to-starch ratio, reaction time, gelatinization of the starch, and reactant concentration in water. At high reactant concentrations, high conversions of methyl acrylate to grafted PMA could be obtained in less than 0.5 h at 25°C. © 1993 John Wiley & Sons, Inc.     

Effect of radiation chemical treatment on sisal fibers I. Radiation induced grafting of ethyl acrylate

Radiation induced graft copolymerization of ethyl acrylate onto sisal fibers was investigated. It was fond that the percent added-on of ethyl acrylate to sisal fibers was prohibitively low when using the direct grafting method due to excessive hompolymerization. The preirradiation method was found to be invalid for improving the grafting content. In the presence of small amounts of styrene (St) the copolymerization can be achieved with little homopolymer formation by the direct grafting technique. The presence of sulfuric acid in the grafting solution enhances the grafting of styrene–ethyl acrylate comonomer to sisal fibers. the effect of different solvents, monomer concentration, and irradiation doses were followed. Sisal fibers were treated with sodium hydroxide, sulfuric acid, and combined treatment of both of them. The effect of these treatments on the grafting content was investigated. The grafting yield decreased when sisal fibers were subjected to alkali treatment under tension. However, sisal fibers pretreated with 0.4N sulfuric acid showed a slight increase in the grafting yield over the untreated samples.     

Functionalisation of polypropylene by solid phase graft polymerisation and its effect on the mechanical properties of silica nanocomposites

Abstract

To prepare macromolecular compatibiliser for grafted nano-SiO₂/polypropylene (PP) composites, solid phase graft copolymers of PP with styrene and ethyl acrylate were synthesised, respectively. It was found that both percentage grafting and grafting efficiency can be adjusted by changing initiator concentration, reaction temperature and reaction time. Due to partial chain scission and deterioration of the ordered structure of PP during the graft polymerisation, the grafted PP exhibits worse thermal stability and crystallisability than the unmodified PP. Mechanical tests of grafted nano-SiO₂/PP composites indicated that the addition of PP copolymer with the same species of grafting polymer as that on the nanoparticles further improves the ductility of the composites. Molecular rigidity of the grafting polymers, presence of the homopolymer produced during the graft polymerisation, and strain rate of the load applied have important influences on the toughening effect of the functionalised PP.     

Functionalisation of polypropylene by solid phase graft polymerisation and its effect on mechanical properties of silica nanocomposites

Abstract

To prepare macromolecular compatibiliser for grafted nano-SiO₂ /polypropylene (PP) composites, solid phase graft copolymers of PP with styrene and ethyl acrylate were synthesised, respectively. It was found that both per cent grafting and grafting efficiency can be adjusted by changing initiator concentration, reaction temperature and reaction time. As a result of partial chain scission and deterioration of ordered structure of PP during the graft polymerisation, the grafted PP exhibits poorer thermal stability and crystallisability than the unmodified PP. Mechanical tests of grafted nano-SiO₂ /PP composites indicated that the addition of PP copolymer with the same species of grafting polymer as that on the nanoparticles further improves the ductility of the composites. Molecular rigidity of the grafting polymers, presence of the homopolymer produced during the graft polymerisation, and strain rate of the load applied have an important influence on the toughening effect of the functionalised PP.     

Synthesis and characterization of oil sorbers based on docosanyl acrylate and methacrylates copolymers

Docosanyl acrylate (DCA) monomer was copolymerized with different monomer feed ratios of cinnamoyloxy ethyl methacrylate (CEMA) or methyl methacrylate (MMA) monomer to produce different compositions for DCA/CEMA or DCA/MMA copolymer with low conversions.¹H NMR spectroscopy was used to confirm the copolymer structure. DCA was crosslinked with different mol % of CEMA or MMA using dibenzoyl peroxide as initiator and various weight percentages of either 1,1,1‐trimethylolpropane triacrylates or 1,1,1‐trimethylolpropane trimethacrylates crosslinkers. The effects of monomer feed composition, crosslinker concentration, and the hydrophobicity of the copolymer units on swelling properties of the crosslinked polymers were studied through the oil absorbency tests. The network parameters, such as polymer solvent interaction (χ), effective crosslink density (υ_e), equilibrium modulus of elasticity (G_T), and average molecular weight between crosslinks (M_c), were determined and correlated with the structure of the synthesized copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008