Graft copolymerization of acrylic acid on cellulose: Reaction kinetics of copolymerization

Acrylic acid (AA) was grafted to cellulose by using ceric ammonium nitrate (CAN) initiator in aqueous nitric acid solution at 30, 50, 70, and 90°C during reaction periods of 30 to 180 minutes. About 45% of the AA was polymerized at 90°C after 180 minutes. The grafted polymer and homopolymer were isolated by acetone from the reaction mixture, dried, and subjected to Soxhlet extraction with dioxane to separate the homopolymer, poly(acrylic acid), from the graft copolymer. The water absorption capacities and grafting values of grafted cellulose were also determined. The maximum grafting yield was obtained at 30°C. It was also observed that polyacrylic acid-grafted cellulose produced at 30°C had the highest water retention capacity. The time dependence of AA conversion allowed calculation of first-order reaction rate constants. These rate constants were then used to determine apparent activation energies. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 929–934, 1997     

Kinetic analysis of the radiation polymerization of methyl methacrylate–kaolin clay composites

In the first of a two-part series, a kinetic study has been made on the effects of gamma rays (⁶⁰Co) in air and inert gas on the polymerization of a 50:50 weight-mixture methyl methacrylate (MMA)–kaolin clay system. The effect of dose rate (7.35–24.9 rads/sec), temperature (25° to 75°C), and total dose on the percentage conversion of monomer to polymer was studied. The rate of formation of polymer at 25°C in the composite system was found to be faster when compared to a bulk MMA system at the same dose rate. This acceleration showed that the clay had a catalytic effect on the formation of polymer. The effect decreased as temperature increased. Two types of poly(methyl methacrylate) (PMMA) were formed in the composite. One type was called homopolymer and could be removed from the composite by extraction with organic solvents. The other type was called inserted polymer and could only be removed by dissolving the clay matrix with hydrofluoric acid. The total polymer conversion was the summation of these two types of polymer formed. The kinetic analysis examined the orders of reaction and activation energies of the homopolymer, inserted polymer, and total polymer. The initial reaction orders of the homopolymer and total polymer based on dose were ?0.46 and ?0.49, respectively. These indicate a definite free-radical reaction. The reaction order of the inserted polymer was temperature dependent. The activation energies for the homopolymer and total polymer in both atmospheres were approximately 1 kcal/mole less than the bulk activation energy at the same conditions. The inserted polymer had an activation energy which was dose rate dependent.     

Factors affecting photografting of methacrylic acid on polyethylene film in liquid phases system

Factors affecting photografting (λ > 300 nm) of methacrylic acid on low-density polyethylene film were investigated in liquid-phase system with water. Benzophenone was used as a sensitizer by coating it on the film surface. Factors examined were monomer concentration (1.3 wt% to 10.0 wt%), polymerization temperature (30°C to 70°C), and film thickness (30 μm and 80 μm). It was found that grafted polymer is formed preferentially as compared with homopolymer under conditions such as monomer concentration higher than 6.0 wt%, polymerization temperature higher than 50°C, and film thickness of 30 μm. The structure of the grafted samples obtained in the above systems was characterized by the grafted chains distributing over the film and the flat appearance of film surface. In the grafting systems using the monomer concentration lower than 6.0 wt%, the polymerization temperature lower than 50°C, and the film thickness of 80 μm, homopolymer was formed predominantly. The resultant grafted chains localized mainly on the film surface, which appeared to be grainy.     

Investigation of thermal behavior of poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) networks

The thermal behavior of poly(2‐hydroxyethyl methacrylate) [PHEMA] homopolymer and poly(2‐hydroxyethyl methacrylate‐co‐itaconic acid) [P(HEMA/IA)] copolymeric networks synthesized using a radiation‐induced polymerization technique was investigated by differential scanning calorimetry, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The glass‐transition temperature (T_g) of the PHEMA homopolymer was found to be 87°C. On the other hand, the T_g of the P(HEMA/IA) networks increased from 88°C to 117°C with an increasing amount of IA in the network system. The thermal degradation reaction mechanism of the P(HEMA/IA) networks was determined to be different from the PHEMA homopolymer, as confirmed by thermogravimetric analysis. It was observed that the initial thermal degradation temperature of these copolymeric networks increased from 271°C to 300°C with IA content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1602–1607, 2007     

Porous polymer carbons. II. Preparation and properties of porous poly(vinylidene chloride) carbons

Suspension–polymerized copolymers of vinylidene chloride and ethylene glycol dimethacrylate have been converted into carbons by heating to 900°C. Poly(vinylidene chloride) homopolymer may melt on a first-stage heating at ca. 200°C and consequently yields a fused 900°C carbon; restraining the first-stage heating to slightly lower temperatures permits the retention of the polymer morphology which is then retained on subsequent carbonization at 900°C. The crosslinked copolymers do not fuse at 200°C and lose the dimethacrylate component, apparently cleanly, in the temperature range of 350–450°C and give 900°C carbons which are shrunken pseudomorphs of the parent polymer; all structural features are retained, including the characteristic skin of the polymer particles. Thus, the macroporous character of the carbons is controlled by both the crosslinker and diluent contents of the original polymerization recipe. The 900°C carbons are also microporous; hysteresis in nitrogen (77°K) isotherms is attributed to activated diffusion since carbon dioxide (196°K) isotherms are reversible. The microporosity of these dual-porosity carbons depends on the content of crosslinking comonomer in the parent polymer, and possible reasons for this dependence are discussed.     

N‐(2‐biphenylenyl)‐4‐[2′‐phenylethynyl] phthalimide: 2. Detailed study of the monomer cure and properties of the resulting polymer

A detailed study is presented of the high‐temperature cure of the difunctional monomer N‐(2‐biphenylenyl)‐4‐[2′‐phenylethynyl]phthalimide (BPP) and the thermal properties of the resulting homopolymer. Although the phenylethynyl groups are consumed within 1 h at 370 °C, other reactions continue well after this, leading to a cured polymer whose glass transition temperature (T_g) is highly dependent on cure time and temperature. A T_g of 450 °C is achieved after a 16 h cure at 400 °C. Use of chemometrics to analyse the infrared spectra of curing BPP provides evidence for changes in the aromatic moieties during cure, perhaps indicative of co‐reaction between the biphenylene and phenylethynyl groups; however, other processes also contribute to the overall complex cure mechanism. Despite the high T_g values, BPP homopolymer exhibits unacceptably poor thermo‐oxidative stability at 370 °C, showing a weight loss of about 50 % after 100 h ageing. This is perhaps a result of formation of degradatively unstable crosslink structures during elevated‐temperature cure. Copyright © 2004 Society of Chemical Industry     

The xanthate method of grafting. V. Graftability of mechanical pulp

Softwood mechanical pulp was copolymerized with acrylonitrile using the xanthate redox grafting process. Experiments carried out under different reaction conditions (temperature, H₂O₂, concentration, pH, reaction time) showed that mechanical pulp is less apt to form graft copolymers than chemical pulps. In most cases, long inhibition periods were observed, and the product formed thereafter contained large quantities of homopolymer. It was not possible to raise grafting efficiency by increasing the concentration of hydrogen peroxide. A series of experiments with pulps having different particle size showed a moderate increase in total conversation to polymer with decreasing mean fiber length. The latter, however, produced little influence on the copolymer/homopolymer ratio.     

DEVELOPMENT OF SYNERGISTIC HEAT STABILIZERS FOR PVC FROM ZINC BORATE-ZINC PHOSPHATE

The importance of flame-retardant and smoke-suppressed poly(vinyl chloride) (PVC) compositions is increasing gradually in the polymer industry since PVC releases smoke and toxic gases (hydrogen chloride, HCl) during heating at temperatures above 140°C with the result of dehydrochlorination reaction. In this study, the synergistic effects of zinc borate (ZB)-zinc phosphate (ZP) on the thermal stability of PVC were investigated using thermal techniques. The induction and stability time values of PVC plastigels were obtained at 140° and 160°C. The results revealed that PVC plastigels having only ZP and ZB retarded dehydrochlorination of PVC compared with the unstabilized sample. However, the plastigels with both ZB and ZP had a superior synergistic effect on char formation of PVC. Since the induction periods of the samples having both ZB and ZP were higher than those of the unstabilized samples having only ZB or only ZP, the synergistic effect was observed.     

Reactivity Toward Phenol of Lignin from the Hydrolysis of Sweetgum Wood with Concentrated Sulfuric Acid

Sweetgum wood was hydrolyzed at 20°C and 50°C for different time periods with 68% sulfuric acid. The lignin residues obtained were subjected to a phenolation reaction. For lignin prepared at the lower temperature the maximum phenol uptake was 9.5%, and at the higher temperature only 5–6%. When wood prehydrolyzed with dilute acid was used the phenol uptake rose to 12.5%. However, all the sulfuric acid hydrolysis lignins showed much lower reactivity toward phenol than the 20% phenol uptake exhibited by lignin isolated using concentrated hydrochloric acid.     

Polymerization of glycidyl methacrylate with poly(ethylene terephthalate) fibers using Fe+2–H2O2 redox system

Fe⁺²–H₂O₂ redox system initiated polymerization reactions of glycidyl methacrylate (GMA) from aqueous solution with poly(ethylene terephthalate) fibers (PET) were investigated. The polymer add-on is greatly influenced by H₂O₂ concentration, GMA concentration, as well as reaction time and temperature. Polymer add-on was directly related to H₂O₂ concentration up to 30 meq/L and GMA concentration up to 4%. Further increase in concentrations of H₂O₂ and GMA resulted in lower polymer add-on. Raising the reaction temperature from 65°C to 95°C caused a significant enhancement in the rate of polymerization, the latter follows the order 95 > 85 > 75 > 65°C. However, at 65°C, the polymerization reaction showed an induction period of about 120 min, in contrast with reactions at 75°C, 85°C, and 95°C, where no induction period was observed though the polymer add-on was quite low at 75°C during the initial stages of the reaction. Using dimethylformamide (DMF) alone or mixed with water as polymerization medium offset the polymerization reaction. Incorporation of thioureadioxide in the polymerization system decreased the polymer add-on significantly.     

Online monitoring of reaction temperature during cationic ring opening polymerization of epichlorohydrin in presence of BF3 and 1,4‐butanediol

This work introduces cationic ring opening polymerization of polyepichlorohydrin (PECH) produced under various reaction conditions (set temperature: ?10 to 40°C, [C]/[I] ratio: 0.1–1, monomer feed rate: 1–4 mL/min). In addition, a correlation between the exothermic reaction temperature and the performance of the PECH was obtained by utilizing a reaction temperature monitoring system, GPC, ¹H‐NMR, and FTIR. During the polymerization, an induction period which affects the polydispersity was observed below 10°C. At lower temperatures and lower [C]/[I] ratios, a higher induction period was observed. The monomer feed rate did not affect the induction period but it highly affected the polydispersity when the induction period occurred. The total molecular weight of PECH increased with decreasing set temperature even though the amount of low molecular weight cyclic oligomer increased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39912.     

Alternating copolymerization of methyl α-phenylacrylate and methyl methacrylate by n-BuLi

The copolymerization of methyl α-phenylacrylate (MPhA) and methyl methacrylate by n-BuLi was carried out in toluene at various temperatures with an initial monomer ratio of 1:1. At ?78°C the product was a homopolymer of MPhA. The copolymer obtained at ?40°C was a mixture of poly(methyl α-phenylacrylate) and poly(methyl methacrylate) containing a small amount of alternating copolymer of both monomers. With further increase in the polymerization temperature the fraction of alternating copolymer increased and above 30°C all the copolymers obtained were alternate. With varying composition of feed monomers the copolymerization was carried out at 30°C and the alternating copolymer was obtained over a wide range of monomer feed ratios. In tetrahydrofuran the alternate sequence began to form at a lower temperature than in toluene, and all the copolymers obtained above 0°C were alternating ones. The mechanism of the copolymerization is discussed in some detail.     

Testing the Antioxidant Effect of Essential Oils and BHT on Corn Oil at Frying Temperatures: a Response Surface Methodology

Food habits worldwide have increased the demand for oxidative-resistant oils that can be used for deep-frying. Oxidative stability in oils can be improved by changing the fatty acid composition of the oil or by adding natural antioxidants to the oil. In this study, the effect of essential oils of seven plants; cinnamon, rosemary, sage, turmeric, clove, thyme and oregano enriched with carvacrol on the oxidative stability of corn oil at frying temperatures were studied. Experiments were conducted by using a PetroOxy device, a rapid small scale oxidation stability test. A central composite design was used to evaluate the effects of concentration of essential oil (X1: 1,500–5,000 ppm) and temperature (X2: 150–180 °C), on the induction time of corn oil. In order to compare the results with the synthetic antioxidant, butylated hydroxy toluene (BHT), another design was made with a concentration range (60–350 ppm) containing the legal upper limit of BHT, 200 ppm. Induction periods obtained from the accelerated oxidation test revealed that increasing temperature decreased the induction time of all the samples. However, the essential oils except for oregano oil had no significant antioxidative effect on corn oil, probably due to a lower content of their active components. The antioxidative effect of oregano oil was also found to be higher compared to BHT. At very high temperatures (e.g., 180 °C), the concentration of antioxidants had no effect on the induction periods.     

Melting and crystallization behavior of copolymer from cyclic butylene terephthalate and polycaprolactone

In this study, we investigated the nonisothermal crystallization kinetics, crystallization morphology, and melting behavior of polymerized cyclic butylene terephthalate (pCBT) copolymerized with polycaprolactone (PCL). The results of this experiment indicated that the Ozawa exponent varied between 2 and 3 for pCBT, but between 1 and 2 for blends of pCBT/PCL. At the same temperature (185°C), the crystallization rate constant K_T for pCBT/PCL blend was much lower than for pCBT homopolymer. These results indicated a strong hindrance on the crystallization of pCBT/PCL blends. The pCBT and pCBT/PCL samples exhibited no visible difference in morphology or microstructure. However, the crystallization and melting peak temperature of pCBT/PCL blends was ～20°C lower than that of pCBT homopolymer. Crystal morphology confirmed that the mechanism of simultaneous polymerization and crystallization found applicable to pCBT homopolymer did not apply for blends of pCBT/PCL. It therefore appears that crystallization should be delayed until after the completion of pCBT/PCL copolymerization. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Ionomer. I. The effect of woven glass mat reinforcement on tensile properties

An investigation was conducted on ionomer polymer. The ionomer pellets were molded into a thin sheet before fabrication into composites. The reinforcing agent used was woven glass mat. Before fabrication, the woven glass mat was treated with the following: 1. silane coupling agent for 5 min and dried at room temperature; 2. silane coupling agent for 5 min and dried in the oven at 110°C for 15 min; 3. Ultraviolet radiation for 5 min; and 4. silane (oven dried + ultraviolet). The composites were fabricated at various pressure, time, and temperature. An ideal processing condition was established, i.e., pressure = 5 MPa, temperature = 180°C, and the impregnation time = 30 min. The void contents of the composites were estimated using the ignition method and the tensile properties were measured. The results revealed that good impregnation of the matrix ionomer into the reinforcing agent can be achieved at 180°C. This was confirmed by low void content as compared with other test temperatures. Further clarification was through the tensile properties, which were higher than those at lower temperatures (120 and 150°C). The effect of fiber orientation was checked, and both 0 and 90° had identical strengths and moduli irrespective of the various fiber treatments. Apart from the void contents, the degree of impregnation was also checked based on the tensile strengths in 45, 25, and 60° fiber orientations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1395–1400, 2001     

Synthesis,characterization and biological activity of 3‐(1‐cyclohexyl)azetidinyl methacrylate monomer and its homopolymer

3‐(1‐Cyclohexyl)azetidiniyl methacrylate (CyAMA), a new methacrylate monomer, was synthesized by reaction of the sodium salt of 1‐cyclohexylazetidin‐3‐ol with methacryloyl chloride. The monomer was polymerized at 60 °C in 1,4‐dioxane solution using 2,2′‐ azobisisobutyronitrile (AIBN) as an initiator. CyAMA and poly(CyAMA) were characterized by FTIR and ¹H and ¹³C NMR spectroscopy. The activation energy of the initiation step of the polymerization was estimated from initial rates, and the number average molecular weight of the homopolymer was determined by gel permeation chromatography (GPC). The antibacterial and antifungal effects of the monomer and homopolymer were investigated on various bacteria and fungi. The thermal stability of poly(CyAMA) was investigated by TGA, and its glass transition temperature was determined by DSC as 93 °C. © 2000 Society of Chemical Industry     

Effect of heat treatment on the synthesis of hydroxyapatite from Indian clam seashell by hydrothermal method

Hydroxyapatite (HA) powder has been successfully synthesized from low-cost Indian clam seashells by using hydrothermal method. The mixture of tri-calcium phosphate [Ca₃(PO₄)₂], heat-treated ball-milled clam seashell, and demineralized water are heat-treated at several temperatures (700 °C, 800 °C, 900 °C, 1000 °C, and 1100 °C) for various time periods (1 h, 2 h, and 3 h) to perform the hydrothermal reactions. The phases and microstructure of the solid-state reaction products are analyzed through X-ray diffraction (XRD) method and field emission scanning electron microscopy (FESEM) respectively. The crystallite size of all the synthesized powders is calculated by using Scherrer's model. Mainly HA phase is obtained in all the different reaction products. However, these HAs are found to be non-stoichiometric in nature. As per the literature, non-stoichiometric HA is a more biologically active material compared to the stoichiometric one. Almost pure HA is formed with any selected reaction temperature applied for 2 h time duration. The crystallinity and Ca/P ratio of the synthesized pure HA are estimated by using standard model and energy-dispersive X-ray spectroscopy (EDS) analysis, respectively. The highest amount of near stoichiometric crystalline HA has been obtained at 900 °C of reaction temperature applied for 2 h time duration. With raising reaction temperature, the grain size of pure HA is found to be increased. Needle/rod shaped nano grains are noticed to form at lower reaction temperature whereas; beyond 1000 ^oC of temperature globular/spherical shaped grains are also observed to form. At 3 h reaction time agglomeration of grains is found to occur in all the synthesized powders.     

Application of the Conant-Finkelstein Reaction to the Modification of PVC: Iodinated PVC

The Conant-Finkelstein reaction was applied to PVC with the aiming of replacing the chlorine atoms with iodine ones. The effect of reaction temperature with regard to the characteristics of the modified PVC was significant. Formation of a gel and degraded polymeric materials was observed when working at temperatures higher than 60 °C. The degraded polymer formed at 70 °C was insoluble and gave rise to a polyacetylene-like chain with a melting point of 60 °C. However, the reaction on PVC at lower temperatures resulted in soluble polymers which were easily amenable to spectral characterization. The molecular weights of the iodine-modified PVCs were temperature-dependent. At 40, 45, 50 and 60 °C, molecular weights lower than that of the initial PVC were measured; however, at 35, 30 and 25 °C, a gain of about 9% in molecular weight was seen. Substitution and elimination reactions occurred to different extents depending mostly on temperature. Optimal substitution was obtained at 50 °C for a reaction time of 20 h.     

The effect of modification on structure and dynamic mechanical behavior during the processing of acrylic fiber to stabilized fiber

Polyacrylonitrile (PAN) fibers pretreated with potassium permanganate have reduced the time required for stabilization, and also improved mechanical properties of the resultant carbon fibers. In this study, the effect of modification on the stabilization process and the dynamic mechanical properties of PAN fibers have been examined. The beta peak appeared at about 125°C on the loss tangent curves caused by molecular motion in the PAN fiber. Appearing at about 254°C, the alpha peak is attributed to chemical reactions and molecular motion in the formation of the crystalline phase of stabilized fibers. The alpha peak of the modified PAN fiber had lower absorption and had a smaller peak in the temperature range of 212–239°C. This indicated that potassium permanganate acts as a catalyst to lower the reaction temperature by about 20°C of the initial cyclization reaction. The dynamic storage modulus analysis indicated that modified PAN fibers have a lower initial transition temperature and that formation of the ladder polymer is gradual and steady.     

The CO-catalyzed conversion of H2S to H2 + sulfur part 2. The thermal decomposition of COS

The pyrolysis of COS has been studied over the temperature range 300 to 750°C using a variety of catalysts. The observed product distribution confirmed that two parallel reaction paths: 2 COS → 2 CO S₂ (2) and 2 COS → CO₂ + CS₂ (4) are involved in the decomposition. The decomposition yield increased with rising temperature, accompanied with a shift in selectivity. At temperatures lower than ～700°C the disproportionation reaction 4 was predominant, whereas at temperatures higher than 700°C, reaction 2 was favoured. In the high-temperature region (700 to 750°C) it was possible to achieve full suppression of reaction 4 with added CS₂. The pyrolysis of COS was also studied in a reactor packed with quartz chips without catalysts at high temperatures. Between 800 and 900°C, up to 99% conversion (with respect to the thermodynamic limit) could be achieved, with the almost complete absence of the disproportionation reaction 4. The results point to the commercial potential in the two-step reaction sequence: for the economic conversion of hydrogen sulfide to hydrogen and sulfur.