Organotin polymers—XVII. Azeotropy in terpolymerization reactions of tri-n-butyltin 4-acryloyloxybenzoate wit alkyl acrylates or styrene and acrylonitrile

Ternary copolymerizations of tri-n-butyltin 4-acryloyloxybenzoate (ABTB) with acrylonitrile (AN) and alkyl acrylates [methyl (MA), ethyl (EA) or butyl acrylate (BA)], methyl methacrylate (MMA) or styrene (ST) were carried out in solution at 70°C in the presence of free radical initiator. Experimental terpolymerization data agreed well with calculations based on the Alfrey-Goldfinger equation. The determination of unitary, binary and ternary azeotropies of various systems studied was easily handled by a computer program. The results obtained show that there is no ternary azeotropic composition for any terpolymer, system studied. Selective unitary and binary azeotropic compositions were polymerized and the results obtained show good agreement between the theoretical and experimental terpolymer composition for each case.     

Terpolymerization reactions of N-acryloyloxyphthalimide or N-methacryloyloxyphthalimide with methyl acrylate,methyl methacrylate and acrylonitrile

Ternary copolymerization reactions of N-acryloyloxyphthalimide (NAP) or N-methacryloyloxyphthalimide (NMP) and acrylonitrile with methyl acrylate or methyl methacrylate were carried out in solution at 60°C in the presence of a free radical initiator. Experimental terpolymerization data agree well with calculations based on the Alfrey-Goldfinger equation. The determination of unitary, binary, and ternary azeotropies of the various systems studied was easily handled by a computer program. The results show that there is no ternary azeotropic composition for any terpolymer system studied. Selective unitary and binary azeotropic compositions were polymerized and the results show good agreement between the theoretical and experimental terpolymer composition in each case. The estimation of terpolymer compositions was carried out by ¹H NMR spectroscopy.     

Azeotropy in terpolymerization of 2-pyrimidyl acrylamide with different alkyl acrylates and acrylonitrile

2-Pyrimidyl acrylamide monomer (2PA) has been prepared by the reaction of 2-amino pyrimidine with acrylolyl chloride in the presence of triethylamine as catalyst. Its structure was confirmed by IR and ¹H NMR spectroscopy. Ternary copolymerizations of 2-pyrimidyl acrylamide monomer (2PA) with methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), butyl acrylate (BuA) and acrylonitrile (AN) were carried out in THF at 65°C in the presence of a free radical initiator. Experimental terpolymerization data agree well with calculations based on the Alfrey–Goldfinger equation. The determination of unitary, binary and ternary azeotropies of the various systems studied were easily handled by a computer. The ternary azeotropic compositions for 2PA–MA–AN and 2PA–MMA–AN were 32.20:17.5:50.30 and 13.54:52.64:33.82mol%, respectively. Pseudo-azeotropic regions were identified where the deviation between feed and polymer composition is very small.     

p-acetyl benzylidene triphenylarsonium ylide initiated radical terpolymerization of styrene,acrylonitrile and copper acrylate: synthesis,characterization and properties

Solution terpolymerization of styrene (Sty), acrylonitrile (AN) and copper acrylate (CuA) has been carried out in dimethylformamide at 90°C for 4 h using p-acetyl benzylidene triphenylarsonium ylide as radical initiator. ¹H nuclear magnetic resonance (NMR), IR and elemental analysis have been used to characterized the terpolymer. Analysis of kinetic data indicates the following rate equation: The overall activation energy is 38 kJ mol⁻¹. The composition of terpolymer calculated from NMR and elemental analysis has been used to evaluate reactivity ratios as r₁(Sty) = 5 ± 2 and r₂(AN + CuA) = 0.4 ± 0.02 employing the Finemann–Ross method, which confirms its random origin. The terpolymer was thermally stable up to 2007deg;C.     

Effect of crosslinker,buffer, and blending on damping properties of poly(styrene‐acrylonitrile)/poly(ethyl acrylate‐ n‐butyl acrylate) latex interpenetrating polymer networks

A series of poly(styrene‐acrylonitrile)/poly(ethyl acrylate‐n‐butyl acrylate) latex interpenetrating polymer networks (LIPNs) are synthesized by changing the kind of crosslinker and introducing a buffer. The results show that the crosslinker has an important effect on the damping properties of the LIPNs; divinylbenzene is the best crosslinker in the study. Moreover, introducing a buffer into LIPNs leads to an increase of the damping values over the temperature range where the damping value surpasses 0.5. The LIPN blend prepared by mixing LIPNs results in broadening of the damping peak, therefore improving the damping properties. Tests of the damping properties show that the LIPNs have good practical value. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2347–2351, 2002     

Control of monodisperse particle size of styrenic–acrylate copolymers in dispersion copolymerization

Syntheses of monodisperse poly[(styrene)‐co‐(n‐butyl acrylate)] and poly[(styrene)‐co‐(2‐ethylhexyl acrylate)] were carried out by dispersion polymerization. The reactions were performed in the mixed solvent of ethanol–water in the presence of azo‐bisisobutyronitrile and poly(N‐vinylpyrrolidone) as the initiator and dispersant, respectively. The effects of reaction parameters, that is the type and concentration of dispersant, ratio of the mixed solvent, reaction temperature, agitation rate, monomer composition between styrene and n‐butyl acrylate or 2‐ethylhexyl acrylate, crosslinking agent and reaction time on the particle size, size distribution and average molecular weights of the resulting copolymer were thoroughly investigated. The resulting copolymer particles were smooth on their spherical surface and the sizes were in the range 0.6–1.8 µm with a narrow size distribution. In most cases, a correlation between small particle sizes with high average molecular weights was observed. The average particle size generally increased with increasing reaction temperature, time and acrylate monomer content. In contrast, the particle size decreased as the molecular weight, concentration of dispersant, polarity of the medium or agitation rate was increased. The glass transition temperature (T_g) of the copolymers can be controlled by the mole ratio of the comonomer. The T_g values decreased when the content of acrylate monomers in the copolymer increased, and T_g values of the synthesized copolymer were in the range 66–102 °C. Instead of using n‐butyl acrylate monomer in the copolymerization, 2‐ethylhexyl acrylate copolymerization with styrene resulted in insignificant changes in the particle sizes but there were significant decreases in T_g values. In this study, the monodisperse particles can be obtained by monitoring the appropriate conditions regarding PVP K‐30 (2–8 wt%), ethanol/water (90/10 wt%), the reaction temperature (70 °C) and the agitation rate (100 rpm). © 2000 Society of Chemical Industry     

Rubber content effect on scratch behavior in acrylonitrile‐styrene‐acrylate copolymers

The scratch behavior of butyl‐acrylate rubber‐modified styrene‐acrylonitrile thermoplastics is investigated following the ASTM D7027 linearly increasing normal load test methodology. The critical normal loads at the onset of the major transitions along the scratch path, such as groove formation, scratch visibility, microcrack formation, and plowing, are reported and quantitatively analyzed. It is found that the scratch resistance generally deteriorates with increasing butyl‐acrylate rubber content, and is strongly related to the tensile and compressive yield stresses of the blends. Microscopy investigation indicates that a rubber content of up to 30 wt % in a styrene‐acrylonitrile copolymer (SAN) does not alter the scratch‐induced damage mechanisms, but only reduces the critical onset loads for the observed damage transitions. The present finding suggests that addition of rubber causes reductions in modulus, tensile, and compressive yield stresses, thus leading to deterioration in scratch resistance. It appears that the improvement in ductility for SAN after the rubber toughening does not benefit scratch resistance. Implication of rubber toughening on scratch behavior of polymers is discussed. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and thermoanalysis of emulsion terpolymers of N‐phenylmaleimide,styrene, and acrylonitrile

Terpolymers of N‐phenylmaleimide (PMI), styrene, and acrylonitrile (AN) were synthesized by emulsion polymerization. The thermal properties of terpolymers at different PMI and AN feed contents were investigated by differential scanning calorimetry, torsional braid analysis, thermogravimetric analysis, and a Vicat softening point test. The results showed the glass‐transition temperature and decomposition temperature of the terpolymers increased with increasing PMI feed content. Furthermore, the Vicat softening point of the terpolymers rose with PMI feed content. The weight‐ and number‐average molecular weights (M̄_w and M̄_n) of the terpolymers were also determined by gel permeation chromatography. The results showed that the M̄_w and M̄_n of the terpolymers decreased with increasing PMI feed content and increased with increasing AN feed content. The mechanical properties (tensile strength and impact strength) of the terpolymers decreased with increasing PMI feed content and increased with increasing AN feed content. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1067–1073, 2001     

Two‐dimensional NMR studies of styrene/n‐butyl acrylate copolymers synthesized by atom transfer radical polymerization

Copolymers of styrene and n‐butyl acrylate were prepared by atom transfer radical polymerization (ATRP) using CuBr/N,N,N′,N′,N″‐pentamethyl‐diethylenetriamine as catalyst and Methyl 2‐bromopropionate as initiator. The polydispersity of the copolymers is quite low (1.1–1.3). ¹³C {¹H} NMR spectra of these copolymers show that the methylene and methine signals of the main chain are compositional sensitive and highly overlapped. Even the distortionless enhancement by polarization transfer (DEPT) was not able to assign the complex and overlapping signals. Assignments of the various resonance signals were done with the help of heteronuclear single quantum coherence (HSQC), total correlation spectroscopy (TOCSY), and heteronuclear multiple bond correlation (HMBC) experiments. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Microstructure,Thermal and Mechanical Behavior of 3D Printed Acrylonitrile Styrene Acrylate

Fused deposition modeling (FDM) is one of the most popular additive manufacturing techniques for polymers. Despite the numerous works on the printability of various types of polymers, there is a lack in understanding the role of the microstructure on the mechanical performance of printed parts. This work aims at addressing this particular point for the case of a polymer that did not receive much attention, namely acrylonitrile styrene acrylate or ASA. This study emphasizes on the effect of the printing temperature on thermal and mechanical performance of printed ASA using differential scanning calorimetry, infra‐red measurements, mechanical testing, X‐ray micro‐tomography, and finite element computation. The experimental results demonstrate a narrow window of printability of ASA based on the thermal response of this polymer during the laying down process. In addition, both experimental and numerical results show an evident loss in the performance that represents one third of the performance of the raw material. Despite this loss, the limited amount of generated porosity and the level of tensile strength of ASA make it a good choice as a feedstock material for FDM compared to other polymers such as acrylonitrile butadiene styrene.     

Kinetics and mechanism of styrene‐acrylonitrile copolymerization in micro‐emulsion

Stable and transparent poly(styrene‐acrylonitrile) latexes were produced by the polymerization of styrene‐acrylonitrile in ternary o/w micro‐emulsions containing sodium dodecyl sulfate as an anionic surfactant. Kinetics of copolymerization was studied at different temperatures using different concentrations of potassium persulfate and hydrogen peroxide/ascorbic acid. The suitability of existing model for homopolymerization was examined for styrene‐acrylonitrile copolymerization after appropriate modification. The latexes were characterized for particle size and number of particles by dynamic light scattering and TEM. The isolated products were characterized by ¹H and ¹³C NMR as well as by thermal analysis. The overall size of particles was found to be between 15 and 20 nm. © 2000 Society of Chemical Industry     

Specific interactions in poly(styrene‐co‐2‐hydroxyethyl acrylate)/poly(styrene‐co‐N,N‐dimethylacrylamide) systems

Amphiphilic copolymers of poly(styrene‐co‐2‐hydroxyethyl acrylate) (SHEA) and poly(styrene‐co‐N, N‐dimethylacrylamide) (SAD) of different compositions were prepared by free radical copolymerization and characterized by different techniques. Depending on the nature of the solvent and the densities of interacting species incorporated within the polystyrene matrices, novel materials as blends or interpolymer complexes with properties different from those of their constituents were elaborated when these copolymers are mixed together. The specific interpolymer interactions of hydrogen bonding type and the phase behavior of the elaborated materials were investigated by differential scanning calorimetry (DSC) and Fourier transform infra red spectroscopy (FTIR). The specific interactions of hydrogen bonding type that occurred within the SHEA and within their blends with the SAD were evidenced by FTIR qualitatively by the appearance of a new band at 1626 cm^?1 and quantitatively using appropriate spectral curve fitting in the carbonyl and amide regions. The variation of the glass transition temperature with the blend composition behaved differently with the densities of interacting species. The thermal degradation behavior of the materials was studied by thermogravimetry. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactive extraction of propionic acid using tri‐n‐octylamine,tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as diluent

BACKGROUND : Propionic acid is widely used in chemical and allied industries and can be produced by biocultivation in a clean and environmentally friendly route. Recovery of the acid from the dilute stream from the bioreactor is an economic problem. Reactive extraction is a promising method of recovering the acid but suffers from toxicity problems of the solvent employed. There is thus a need for a non‐toxic solvent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. RESULTS: The effect of different extractants (tri‐n‐butylphosphate (TBP), tri‐n‐octylamine (TOA) and Aliquat 336) and their mixed binary solutions in sunflower oil diluent was studied to find the best extractant‐sunflower oil combination. Equilibrium complexation constant, K_E, values of 4.02, 3.13 and 1.87 m³ kmol^?1 were obtained for propionic acid extraction using Aliquat 336, TOA and TBP, respectively, in sunflower oil. The effect of different modifiers (1‐decanol, methylisobutyl ketone, butyl acetate and dodecanol) on the extraction was also studied and it was found that modifiers enhance extraction, with 1‐decanol found to be the best. CONCLUSION: The problem of toxicity in reactive extraction can be reduced by using a non‐toxic diluent (sunflower oil) or a modifier in a non‐toxic solvent, with the extractant. The addition of modifiers was found to improve the extraction. Copyright © 2008 Society of Chemical Industry     

Effect of compatibilizer in acrylonitrile‐butadiene‐styrene toughened nylon 6 blends: Ductile–brittle transition temperature

The ductile–brittle transition temperatures were determined for compatibilized nylon 6/acrylonitrile‐butadiene‐styrene (PA6/ABS) copolymer blends. The compatibilizers used for those blends were methyl methacrylate‐co‐maleic anhydride (MMA‐MAH) and MMA‐co‐glycidyl methacrylate (MMA‐GMA). The ductile–brittle transition temperatures were found to be lower for blends compatibilized through maleate modified acrylic polymers. At room temperature, the PA6/ABS binary blend was essentially brittle whereas the ternary blends with MMA‐MAH compatibilizer were supertough and showed a ductile–brittle transition temperature at ?10°C. The blends compatibilized with maleated copolymer exhibited impact strengths of up to 800 J/m. However, the blends compatibilized with MMA‐GMA showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2643–2647, 2003     

4‐Acetamidophenyl acrylate copolymers with acrylonitrile and N‐vinyl‐2‐pyrrolidone: Synthesis,characterization, and reactivity ratios

4‐Acetamidophenyl acrylate (APA) was synthesized and characterized by IR, ¹H and ¹³C NMR spectroscopies. Homo‐ and copolymers of APA with acrylonitrile (AN) and N‐vinyl‐2‐pyrrolidone (NVP) were prepared by a free radical polymerization. All the copolymer compositions have been determined by ¹H NMR technique, and the reactivity ratios of the monomer pairs have been evaluated using the linearization methods Fineman–Ross, Kelen–Tudos, and extended Kelen–Tudos. Nonlinear error‐in‐variable model (EVM) method was used to compare the reactivity ratios. The reactivity ratios for copoly(APA–AN) system were APA(r₁) = 0.70 and AN(r₂) = 0.333, and for copoly(APA–NVP) system the values were APA(r₁) = 4.99 and NVP(r₂) = 0.019. Thermal stability and molecular weights of the copolymers are reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1919–1927, 2006     

Radical polymerization in disperse systems,by J. Bartoň, I. Capek. Ellis Horwood Ltd,Chichester/VEDA,Bratislava, 1994. pp. 352, price £68. ISBN 0-13-752353-X

Radical copolymerization of zinc acrylate (ZnA₂) with acrylonitrile (AN), initiated by As₂S₃–styrene complex(I), in dimethyl Sulphoxide (DMSO) at 90 ± 0.1°C for 1.0h under inert atmosphere, yields non-alternating copolymers. The kinetic expression is R_p ∝ [I]^0.33 [ZnA₂]^0.25 [AN]^0.44, i.e. the system follows non-ideal kinetics, which is due to primary radical termination as well as degradative chain transfer reactions. The values for activation energy (E) and k²_p/k_t are 128kJ mol⁻¹ and 8.57 × 10⁻⁷ litre mol⁻¹ s⁻¹, respectively. Thermal stability, solubility in different solvents, and IR and NMR spectra have been evaluated.     

Mechanical and UV‐shielding properties of in situ synthesized poly(acrylonitrile‐butadiene‐styrene)/zinc oxide nanocomposites

A series of poly(acrylonitrile‐butadiene‐styrene)/ZnO nanocomposites with different ZnO nanoparticles content were synthesized by a mass‐suspension polymerization process. Nanocomposites obtained through this technique presented high impact resistance despite the presence of agglomerates for high ZnO nanoparticles content so that, these samples were subjected to twin‐screw extrusion. The extrusion led to a dramatic morphological change and increased in impact resistance, higher than 100% in most of the cases. On the other hand, the higher the ZnO content, the higher the UV blocking (>95% for 1 and 3% of ZnO) for both materials, before and after extrusion. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Valeric acid extraction with tri‐n‐butyl phosphate impregnated in a macroporous resin: II. Studies in fixed bed columns

Extraction and back‐extraction of valeric acid in a fixed bed packed with Amberlite XAD‐4 resin impregnated with tri‐n‐butyl phosphate were experimentally studied at 25 °C. The effects of the feed flow rate, acid concentration in the feed solution and extractant concentration in the impregnated resin on the breakthrough curves, were investigated. The bed saturation capacity was larger under the conditions of higher extractant concentration in the resin phase and higher acid concentration in the feed solution. A dynamic model that considers intraparticle diffusion and external liquid film diffusion as limiting steps in mass transfer rates was successfully applied. The intraparticle effective diffusivities (10^?9 dm² s^?1) were from one to three orders of magnitude lower than the diffusivities in the external liquid film (10^?8–10^?6 dm² s^?1). A fast and complete back‐extraction of valeric acid from the saturated bed was carried out with sodium hydroxide solutions. The operational life of the impregnated resin was also studied. Copyright © 2005 Society of Chemical Industry     

Study on micellization of poly(N‐isopropylacrylamide‐butyl acrylate) macromonomers in aqueous solution

A kind of thermo‐sensitive macromonomer, styrene‐terminated poly(N‐isopropylacrylamide‐butyl acrylate) [P(NIPAm‐BA)] has been synthesized in this work. With the help of ultraviolet spectrum (UV), proton nuclear magnetic resonance (¹H‐NMR), potentiometric titration and dynamic light scattering (DLS), the molecular structure, thermo‐sensitive characteristics, and micellization behaviors of this kind of macromonomer have been investigated. The obtained results demonstrate that, the molecular structure of thermo‐sensitive macromonomer, including the content of comonomer unit on the backbones and the variety of terminal groups, has great influence on its low critical solution temperature (LCST) and critical micelle concentration (CMC). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reactive extraction of itaconic acid using tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as a non‐toxic diluent

Itaconic acid finds a place in various industrial applications. It can be produced by biocultivation in a clean and environment friendly route but recovery of the acid from the dilute stream of the bioreactor is an economic problem. Reactive extraction is a promising method to recover carboxylic acid but suffers from toxicity problems of the diluent and extractant employed. So there is need for a non‐toxic extractant and diluent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. Effect of different extractants: tri‐n‐butylphosphate (TBP) (an organophosporous compound) and Aliquat 336 (a quaternary amine) in sunflower oil was studied to find the best extractant–sunflower oil combination. Equilibrium complexation constant, K_E, values of 1.789 and 2.385 m³ kmol^?1, respectively, were obtained for itaconic acid extraction using TBP and Aliquat 336 in sunflower oil. The problem of toxicity in reactive extraction can be reduced by using a natural non‐toxic diluent (sunflower oil) with the extractant. Copyright © 2010 Society of Chemical Industry