Polymerization of epoxidized soybean oil with maleinized polybutadiene

Epoxidized soybean oil (ESO) triglycerides were reacted with maleinized polybutadiene (MMPBD) to give plant‐oil‐based thermoset polymers. MMPBD samples were of two different molecular weights [high‐molecular‐weight maleinized polybutadiene (MMPBD‐H), maleate content = 10%, number‐average molecular weight (M_n) = 9000, and low‐molecular‐weight maleinized polybutadiene (MMPBD‐L), maleate content = 15%, M_n = 5000]. To increase the crosslink density of the product, a free‐radical initiator, benzoyl peroxide, was added to this mixture to further crosslink MMPBD through its double bonds. The characterizations of the products were done by dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis, and IR spectroscopy. The ESO–MMPBD polymers were crosslinked rigid infusible polymers. ESO–MMPBD‐H–1 : 1 and ESO–MMPBD‐L–1 : 1 showed glass‐transition temperature values at −23, 78 and −17, 64°C, respectively, whereas the storage moduli of the two polymers at 25°C were 13 and 16 MPa, respectively. The storage moduli of the polymers remained the same or decreased with the addition of a free‐radical initiator. The storage moduli also decreased with increasing ESO concentration above a 1 : 1 epoxy‐to‐anhydride molar ratio. The surface hardness increased dramatically, and the equilibrium swelling ratio decreased with the addition of free‐radical initiator. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Kinetics and modeling of the diffusion‐controlled diallyl terephthalate polymerization

Free radical polymerization kinetics of diallyl terephthalate in bulk was investigated in a wide temperature range from 50°C to 150°C with four different peroxide initiators. Conversion points were measured using Fourier Transform Infrared (FTIR) measurements. The initiator efficiencies and the initiator decomposition rate constants were evaluated from special experiments, applying the theory of dead end polymerization. In addition, the ratios between the degradative and the effective kinetic rate constants to propagation rate constants were obtained from molecular weight measurements at various initiator concentrations. The ratio of chemically controlled termination and propagation rate constant k/k_tc of the polymerization system was obtained using the initial rates of polymerization and the number average molecular weight data between 0.25 · 10^?3 and 15.7 · 10^?3 L mol^?1 s^?1. The glass transition temperature of the polymer, 191°C, was measured by the Alternating Differential Scanning Calorimetry (ADSC) technique. Computed conversions from the developed kinetic model were in good agreement with the conversion and molecular weight measured data. The values of diffusion controlled propagation and termination rate constants k_td0 and k_pd0 with clear and physical meaning were the only two parameters obtained from the developed kinetic model fitting. Polym. Eng. Sci. 44:2005–2018, 2004. © 2004 Society of Plastics Engineers.     

Initiation system effects in the cationic copolymerization of tetrahydrofuran (THF)

Summary Macromonomeric peroxy initiator, poly tetrahydrofuran (poly-THF=inimer) were synthesized via cationic polymerization of THF by the mono- (t-BuBP) and tetra-bromo methyl benzoyl peroxides (BDBP)/ZnCl₂ initiating system. The macromonomers were characterized by ¹H-NMR, IR, and GPC techniques. Methyl methacrylate (MMA) polymerization initiated by poly-THF inimers at 80°C and different times in bulk gave crosslinked poly-THF-b-polymethyl methacrylate block copolymers. Swelling ratios of the crosslinked block copolymers obtained by taking in same amounts of poly-THF inimer and MMA monomer in CHCl₃ were decreased versus time. It was compared the results obtained from t-BuBP-, BDBP-ZnCl₂ initiating systems with t-BuBP-, BDBP-AgSbF₆ initiating systems for THF monomer. Poly(THF-b-MMA) crosslinked block copolymers containing undecomposed peroxide groups initiated the thermal polymerization of styrene, S, were used to obtain poly(THF-b-MM_A-b-S) crosslinked multicomponent copolymers at 90°C. The crosslinked multi component copolymers were investigated sol-gel analysis and swelling ratios in CHCl₃. "Active" poly(THF-b-MM_A) having peroxygen group were used in the free radical coupling reaction of poly butadien (Poly Bd). Poly(THF-b-MM_A)-polybutadien crosslinked blend soluble graft copolymers were obtained. Received: 31 July 2001/Revised version: 16 June 2002/ Accepted: 5 July 2002     

Peroxide‐controlled degradation of polypropylene using a tetra‐functional initiator

The purpose of this work is to evaluate a new tetra‐functional peroxide initiator and offer comparisons with a di‐functional peroxide commonly used in the production of controlled‐rheology polypropylene (CRPP) resins. CRPP resins have been produced by reactive processing in a batch mixer by using various equivalent amounts of a tetra‐functional and a conventional di‐functional peroxide at two different temperatures. At a lower processing temperature (200°C), the chain length of CRPP decreases with increasing initiator concentration of the di‐functional initiator, while in the case of tetra‐functional initiator system, the change of chain length is larger than that in the di‐functional initiator system. At a higher temperature (230°C), the observation is reversed. The molecular weight reduction increases with initiator concentration level for the tetra‐functional initiator, while the di‐functional initiator causes larger reduction in the molecular weight without any obvious relation to the initiator concentration level. Rheological measurements show results consistent with those from gel permeation chromatography (GPC). The observations are explained based on the competition between chain scission and chain extension caused by the single and multiple radicals generated from the initiators. No evidence of architectural change in the CRPP molecules such as branching and crosslinking has been observed in both GPC and rheological measurements. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Polymerization of acrylamide in inverse microemulsion in the presence of mixtures of oleophilic and hydrophilic surfactants

The preparation of single-phase toluene/sodium bis(2-ethylhexyl)sulfosuccinate(AOT)/water/acrylamide/sodium dodecyl sulfate(SDS) inverse microemulsions is described and their properties prior to polymerization (macroviscosity as a function of volume fraction Φ_aw of the dispersed aqueous (water + acrylamide(AAm) + SDS) phase, and of SDS/AAm mass ratio) are studied. At 20°C three viscosity maxima are observed. At 50°C all three peaks remain, the viscosity of the first and third peak, respectively, is lowered to 5–8 mPa· s while the second, most prominent peak still marks the level of ca. 250 mPa· s. The polymerization of acrylamide in dispersion systems is initiated by water-soluble ammonium peroxodisulfate (APS) and oilsoluble dibenzoyl peroxide (DBP) at 60°C. The polymerization rate of acrylamide for a given [toluene]/[AOT] molar ratio and AAm/water mass ratio monotonically decreases for Φ_aw values greater than 20%. The polyacrylamide viscosity molecular mass increases up to a Φ_aw value of ca. 30%, irrespective of the nature of initiator. For Φ_aw values over 30% the viscosity molecular mass of polyacrylamide seems to level off with some sings of shallow minimum close to Φ_aw of 50%.     

Physicochemical characteristics of acrylic-acid polymer-impregnated cement pastes

Various Portland cement pastes were made using water cement ratios of 0·20, 0·25, 0·35 or 0·40 and then cured for 1, 3, 7, 28, 90 or 180 days. These pastes were impregnated with acrylic acid monomer under vacuum and the monomer-impregnated samples were then treated at two different temperatures, 40 or 60°C, for the polymerization process, using benzoyl peroxide as initiator. Several physicochemical studies were carried out on each cement paste; these studies include compressive strength tests, bulk density, compressive strength versus gel/space ratio relationships, polymer load, X-ray diffraction analysis and differential thermal analysis. Results have indicated that compressive strength improvement in acrylic acid-polymer impregnated cement pastes is mainly dependent on initial water/cement ratio, curing time and gel/space ratio. The results of X-ray diffraction analysis and differential thermal analysis indicated that the intrusion of polymer into the cement paste matrix does not affect the phase composition of the Portland cement hydration products.     

Mechanical properties of uncrosslinked and crosslinked linear low‐density polyethylene/wax blends

The mechanical properties of uncrosslinked and crosslinked linear low‐density polyethylene (LLDPE)/wax blends were investigated, using differential scanning calorimetry (DSC), tensile testing, and melt flow indexing. A decrease in the degree of crystallinity, as determined from the DSC melting enthalpies, was observed with an increase in the dicumyl peroxide (DCP) concentration. The Young's modulus increased with increased wax portions, and there was a higher increase for crosslinked blends. The yield stress generally decreased with increased peroxide content. Crosslinking caused an increase in elongation at yield, but increased wax content caused a decrease in elongation at yield. The stress at break generally increased with increasing peroxide content, but it decreased with increased wax content. The elongation at break decreased with an increase in the DCP concentration. Melt flow rate measurements indicated a mutual miscibility in LLDPE/wax blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 973–980, 2001     

Creep and Dynamic Mechanical Analysis Studies of Peroxide‐Crosslinked Ethylene‐Octene Copolymer

An ethylene‐octene copolymer (EOC) (45 wt% octene) is crosslinked using dicumyl peroxide (DCP). Differential scanning calorimetry (DSC) reveals a very low melting temperature (50 °C). The network density is evaluated by gel content. While 0.2–0.3 wt% of peroxide leads only to a molecular weight increase (samples completely dissolved in xylene), 0.4–0.6 wt% of peroxide caused network formation. High‐temperature creep was measured at 70, 120, and 200 °C at three stress levels. At 200 °C and above 0.6 wt% of peroxide, degradation due to chain scission is observed by rubber process analyzer (RPA) and is again supported by creep measurements. Residual strain at 70 °C is found to improve with increasing peroxide level. Dynamic mechanical analysis (DMA) reveals a strong influence of peroxide content on storage modulus and tan δ, in particular in the range 30–200 °C.

     

Anomalous penetrant transport in glassy polymers V. Cyclohexane transport in polystyrene

Transport of liquid cyclohexane through well characterized, initially glassy, crosslinked polystyrene slabs was investigated. The samples were produced by bulk polymerization of styrene and divinyl benzene using benzoyl peroxide as an initiator at 90°C for 48 h; they had initial crosslinking ratios, X, between 0.005 and 0.025 mol DVB/mol styrene, initial thickness of 0.25 mm to 1.80 mm, and the aspect ratio was maintained above 10 to achieve one-dimensional transport. The results of cyclohexane uptake as a function of time were used to elucidate the effects of degree of crosslinking and sample geometry on the mechanisms of penetrant transport. These results were interpreted in terms of relaxational and diffusional mechanisms.     

Functional copolymers of p‐cumyl phenyl methacrylate and glycidyl methacrylate: Synthesis,characterization, and reactivity ratios

Free‐radical polymerization of p‐cumyl phenyl methacrylate (CPMA) was performed in benzene using bezoyl peroxide as an initiator at 80°C. The effect of time on the molecular weight was studied. Functional copolymers of CPMA and glycidyl methacrylate (GMA) with different feed ratios were synthesized by free‐radical polymerization in methyl ethyl ketone at 70°C, and they were characterized by FTIR and ¹H‐NMR spectroscopy. The molecular weights and polydispersity indexes of the polymers and copolymers were determined by gel permeation chromatography. The copolymer composition was determined by ¹H‐NMR. The glass‐transition temperature of the polymer and the copolymers was determined by differential scanning calorimetry. The reactivity ratios of the monomers were determined by the Fineman–Ross and Kelen–Tudos methods. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 336–347, 2005     

Study of crosslinking of polyphosphazene with allyl pendant groups initiated by benzoyl peroxide

A selected polyorganophosphazene containing three substituents: phenoxy group, 2‐allylphenoxy group, and ethoxy group, had been thermally cross‐linked. The polymer can be crosslinked at 85°C which was lower than the general reported operation temperature. The transformation of chemical structure was analyzed by FTIR technique. It was found that oxidization caused the formation of peroxides, ether and ester during crosslinking. The effect of different conditions including time, temperature, and initiator on properties of crosslinked polymer had been studied. The change of properties was well consistent with the change of chemical structure including vinyl and peroxide. Detailed cross‐linking mechanisms were proposed based on FTIR spectra by monitoring the possible association sites. It was suggested that the initiation reaction preferentially occurred at methylene but not vinyl, and major linkages between polymer chains were ether and peroxide bonds. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Peroxide crosslinking of ethylene–vinyl acetate copolymer

The work reported here concerns the peroxide crosslinking of ethylene–vinyl acetate rubber. Calculated values for scission-to-crosslinking ratios are higher for EVA than for low-density polyethylene. In the temperature range from 150 to 200°C at a constant peroxide content, a rise in temperature results in a decrease in the obtained gel content. Some tensile and modulus–temperature results on crosslinked EVA samples are also reported on.     

Thermosetting polymers from cationic copolymerization of tung oil: Synthesis and characterization

The cationic copolymerization of tung oil with the divinylbenzene comonomer initiated by boron trifluoride diethyl etherate produces promising plastics. The gel times are largely dependent on the relative composition and the reaction conditions and vary from a few seconds to 1 h. Controlled reactions producing homogeneous materials can be obtained by (1) lowering the reaction temperature or (2) decreasing the initiator concentration to less than 1 wt % or (3) adding a certain amount of a less reactive oil, such as soybean oil, low saturation soybean oil (LoSatSoy), or conjugated LoSatSoy to the reaction. The resulting polymers are rigid and dark brown in color. The weight % of the starting materials converted to the crosslinked polymer is ∼85–98% as determined by Soxhlet extraction with methylene chloride. The structure of the bulk product is that of a crosslinked polymer network plasticized by a small amount of low molecular weight oil. The chemical composition of the bulk polymers varies with the original composition of the tung oil system. Dynamic mechanical analysis shows that the resulting products are typical thermosetting polymers with densely crosslinked structures. The modulus of the plastics is approximately 2.0 × 10⁹ Pa at room temperature. One broad glass transition is observed at approximately 100°C. Thermogravimetric analysis shows that the tung oil polymers are thermally stable below 200°C with a 10% weight loss in air around 430°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1044–1056, 2000     

Performance evaluation of silane crosslinking of metallocene‐based polyethylene–octene elastomer

Vinyl trimethoxysilane (VTMS) was grafted onto metallocene‐based polyethylene–octene elastomer (POE) using a free‐radical reaction of VTMS and dicumyl peroxide as an initiator, and then the grafted POE was crosslinked in the presence of water. The effects of VTMS concentration on crystallization behavior, mechanical properties, and thermal properties of POE before and after crosslinking were studied in this article. Multiple melting behaviors were found for POE after silane crosslinking by using DSC measurement. Degree of crystallization of silane‐crosslinked POE decreases from 18.0 to 14.3%, with increase of VTMS from 0 to 2.0 phr. Tensile strength of silane‐crosslinked POE reaches a maximum of 28.4 MPa when concentration of VTMS is 1.5 phr, while elongation at break is 487%. TG shows that the temperature of 10% weight loss for pure POE is 405°C, while for crosslinked POE with addition of 2.0 phr VTMS the value comes to 452°C, indicating that crosslinking significantly help improve the thermal stability of POE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5057–5061, 2006     

Synthesis,characterization, and thermal properties of copolymers of behenyl acrylate and behenyl fumarate

Radical copolymerization of behenyl (systematic IUPAC nomenclature: n‐docosyl) acrylate and behenyl fumarate has been carried out in toluene at 70°C using benzoyl peroxide as initiator. Gel permeation chromatography was used to determine molecular weights (MW) and molecular weight distribution (MWD) of behenyl acrylate–behenyl fumarate (BA‐BF) copolymers. ¹H NMR and carbon analysis was used to determine the composition of BA‐BF copolymers. Monomer reactivity ratios for high conversion polymerization were calculated by conversion‐extended Kelen‐Tudos plot. Differential scanning calorimetric (DSC) measurements shows sharp melting peaks at about 64°C. Thermal stability studies were performed with thermogravimetric analyzer (TGA). By using these DSC and TGA data in several nonisothermal methods, the activation energies were calculated. X‐ray diffraction studies show the linearity of the copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2721–2726, 2003     

Synthesis and characterization of air‐stable magnetic Fe composites microspheres of narrow size distribution

Air‐stable Fe magnetic nanoparticles entrapped within carbon and porous crosslinked polystyrene microspheres of narrow size distribution were prepared by the following sequential steps: (1) Polystyrene/poly(divinyl benzene) and polystyrene/poly(styrene‐divinyl benzene) uniform micrometer‐sized composite particles were prepared by a single‐step swelling of uniform polystyrene template microspheres dispersed in an aqueous continuous phase with emulsion droplets of dibutyl phthalate containing the monomers divinyl benzene and styrene and the initiator benzoyl peroxide. The monomers within the swollen polystyrene template microspheres were then polymerized by raising the temperature to 73°C; (2) Porous poly (divinyl benzene) and poly(styrene‐divinyl benzene) uniform crosslinked microspheres were prepared by dissolution of the polystyrene template part of the former composite particles; (3) Uniform magnetic poly(divinyl benzene)/Fe and poly(styrene‐divinyl benzene)/Fe composite microspheres were prepared by entrapping Fe(CO)₅ within the porous crosslinked microspheres, by suction of the Fe complex into the dried porous particles, followed by decomposition of the encapsulated Fe(CO)₅ at 200°C in Ar atmosphere; (4) Uniform magnetic air‐stable C/Fe composite microspheres were prepared similarly, apart from changing the decomposition temperature from 200 to 600°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Graft copolymerization of lignosulfonate and styrene

A study was made of the graft copolymerization of calcium lignosulfonate with styrene. Heterogenous copolymerization were carried out with methanol as swelling medium, using ferrous ion as catalyst, and ozone and/or hydrogen peroxide as initiator. When using peroxide alone as initiator, monomer conversion was low; after ozonization of lignosulfonates, monomer conversion increased considerably and the grafting efficiency, as well as degree of lignosulfonate grafted, was improved. At 55°C, a 10-fold increase in conversion was observed for reactions with ozone-pretreated lignosulfonates. The investigated factors that affected the graft copolymerization were: the amount of peroxide and ozone charged, the reaction temperature and the ratio of styrene/methanol.     

Polymerization of methyl methacrylate in water in presence of some egyptian sands and quartz pegmatite

The polymerization of methyl methacrylate was carried out in water in presence of some Egyptian sands and quartz pegmatite using sodium bisulphite as initiator. The polymerization was performed at 30, 40, 50 and 60°C using initiator concentrations varying from 0.05 to 0.3 mol/l. The overall rates of polymerization increased from 2.0 × 10^?5 mol/l·s to 4.8 × 10^?5 mol/l·s in presence of quartz pegmatite, to 5 × 10^?5 mol/l·s when Natron sand was used and to 6.4 × 10^?5 mol/l·s in the presence of Ahram sand, as the concentration of each was varied from 0 to 30 g/l. The effect of change of temperature, initiator and monomer concentration on the overall rate of polymerization was studied. The molecular weights were determined viscosimetrically. It was found that the average molecular weights of the obtained polymers increase with the increase of both monomer and initiator concentrations and decrease with rise of temperature. Ahram sand leads to a higher polymer yield and a lower average molecular weight than in case of Natron sand. The stereoregularity of the obtained polymers was determined with a 60 MHz NMR spectrometer.     

Silane‐modified poly(ethylene‐co‐vinyl acetate): influence of comonomers on peroxide‐initiated vinylsilane grafting

Functionalization of poly(ethylene‐co‐vinyl acetate) (EVA) with vinyltriethoxysilane (VTEOS) has been carried out by a free‐radical melt‐grafting procedure in the presence of added comonomers. The influence of comonomers on silane graft yield and crosslink density has been assessed. Experiments were performed on masterbatches of EVA, VTEOS (5 wt %), peroxide initiator (L‐231, 0.05 wt %), and comonomer (0–1 comonomer : VTEOS mole ratio) prepared at 90°C. Melt‐grafting experiments were carried out at 145°C in an oscillating disk rheometer (ODR), which measured crosslink density during the grafting process. Silane graft yields were determined by proton NMR spectroscopy. Comonomers evaluated were maleic anhydride (MAn), 1‐vinyl‐2‐pyrrolidone (VP), and 1‐dodecene (DD). At the comonomer ratios examined, MAn suppressed both silane grafting and peroxide‐initiated crosslinking. Both VP and DD, however, exhibited greater selectivity in suppressing crosslinking than silane grafting; optimum performance was found at a comonomer : vinylsilane mole ratio of 0.2. None of the comonomers studied enhanced the level of silane grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1308–1314, 2000     

Anomalous penetrant transport in glassy polymers VI. Effect of temperature on transport

Transport of liquid cyclohexane through well characterised, initially glassy, crosslinked polystyrene slabs was Investigated at 20, 30, 40, and 50°C. The samples used were produced by bulk polymerization of styrene and divinyl benzene (DVB) at 90°C for 43 hr using benzoyl peroxide as an initiator. The samples tested had initial cross-linking ratios, X, between 5 and 25 × 10^?3 mol DVB/mol styrene. The initial thickness of the samples tested varied from 0.25 mm to 1.80 mm, and the aspect ratio (length to thickness ratio) was maintained above 10;1 in order to analyze the results by one-dimensional transport equations. Cyclohexane uptake was followed as a function of time along with dimensional changes in the thickness and area of the samples. The results of penetrant uptake as a function of time were analyzed using a simplified exponential expression and employing all the data points from the beginning of the experiment until the time of observation of the maximum in uptake. Good correlations were established between the penetrant uptake and the transport temperature. These results were interpreted in terms of competitive relaxational and diffusional mechanisms.