Starve fed emulsion copolymerization of vinyl acetate and 1‐hexene at ambient pressure

A novel emulsion copolymer of vinyl acetate (VAc) and 1‐hexene was synthesized at ambient pressure. The feeding technique, initiation system and reaction time of the copolymerization were optimized based on molecular characteristics such as the weight contribution of 1‐hexene in the copolymer chains and glass transition temperature (T_g) as well as on bulk properties like minimum film‐formation temperature (MFFT) and solid content. According to nuclear magnetic resonance spectroscopy and differential scanning calorimetry results, the combination of starve feeding and redox initiation, within a reaction time of 4 h, effectively led to the copolymerization at ambient pressure between highly reactive polar VAc monomers and non‐polar 1‐hexene monomers of low reactivity. The copolymer showed a lower T_g and MFFT, and a reasonable solid content compared to the poly(vinyl acetate) (PVAc) homopolymer. The consumption rate, hydrolysis of acetate groups and chain transfer reactions during the polymerization were followed using infrared spectroscopy. Based on the results, the undesirable reactions between the VAc blocks were hindered by the neighbouring 1‐hexene molecules. Tensile testing revealed an improvement in the toughness and elongation at break of VAc–1‐hexene films compared to PVAc films. © 2014 Society of Chemical Industry     

Dynamic mechanical properties in blends of poly(styrene‐b‐isoprene‐b‐styrene) with aromatic hydrocarbon resin

The damping properties in blends of poly(styrene‐b‐isoprene‐b‐styrene) (SIS) and hydrogenated aromatic hydrocarbon (C₉) resin were investigated by dynamic mechanical analysis. SIS exhibited two independent peaks of loss factor (tan δ) corresponding to the glass transition of polyisoprene (PI) and polystyrene (PS) segments, respectively. The addition of hydrogenated C₉ resin had a positive impact on the damping of SIS. With the increasing softening point and content of the resin, the main tan δ peak shifted to higher temperatures and the useful damping temperature range was broadened. Addition of mica or PS was found to widen the effective damping range evidently in the high‐temperature region, especially when PS was mixed in the solid state. It was concluded that the dispersed PS domains played a role of reinforcing fillers at low temperatures and served as a polymer component with a tan δ peak due to its glass transition at the high temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4157–4164, 2006     

Cross‐linking of ethylene‐octene copolymer (EOC) by dicumyl peroxide (DCP)

Ethylene‐octene copolymer (EOC) was crosslinked by dicumyl peroxide (DCP) at various temperatures (150–200°C). Six concentrations of DCP in range 0.2–0.7 wt % were investigated. cross‐linking was studied by rubber process analyzer (RPA) and by differential scanning calorimetry (DSC). From RPA data analysis real part modulus s', tan δ, and reaction rate were investigated as a function of peroxide content and temperature. The highest s'_max and the lowest tan δ were found for 0.7% of DCP at 150°C. Chain scission was analyzed by slope analysis of conversion ratio, X in times after reaching the maximum. Less susceptible to chain scission are temperatures in range 150–170°C and peroxide levels 0.2–0.5%. Heat of reaction was analyzed by DSC at various heating rates (5–40°C min⁻¹). It was found to be exothermic. By projection to zero heating rate, the reaction was found to start at 128°C with the maximum at 168°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Copolymers of 3,3,3‐trifluoropropene and vinyl acetate: Synthesis,characterization, and hydrolysis

Copolymers based on 3,3,3‐trifluoropropene (TFP) and vinyl acetate (VAc) were synthesized in supercritical carbon dioxide(sc? CO₂). The copolymers were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and differential scanning calorimetry (DSC) as the thermal analysis method. The copolymer compositions were estimated by three techniques: mass balance, NMR and electric potential analysis. The mole fraction of TFP in the copolymer increased with the feeding TFP added from 12.1% to 76.4% and almost unchanged with a feeding TFP increase from 76.4% to 89.7%. After partial carboxyl groups turned to hydroxyl groups by hydrolysis, the P(TFP‐co‐VAc) copolymer turned into terpolymers, P(TFP‐VAc‐VA). Dispersed in water, the hydrolyzed copolymer obtained emulsion by self‐emulsifying. The size distribution and the morphology of the latex were also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Emulsion copolymerization of vinyl acetate and 2‐ethyl hexyl acrylate using nonionic emulsifiers in loop reactor

Batch emulsion copolymerization of vinyl acetate and 2‐ethyl hexyl acrylate (VAc/2EHA = 90 : 10) was initiated by the thermal initiators ammonium persulfate and potassium persulfate at 70°C in the presence of nonylphenol ethoxylates with varying chain lengths and poly(vinyl alcohol). VAc–2EHA copolymer latexes were synthesized as two different series in a loop reactor. The first series was initiated by ammonium persulfate, and the second series was initiated by potassium persulfate. The influence of the counterions or initiators and chain lengths of a nonionic emulsifier on the properties of VAc–2EHA copolymer latexes were determined by measuring the viscosities, weight‐average molecular weights, number‐average molecular weights, molecular weight distribution, and surface tension of latexes to air. The results for the copolymer latexes indicated that some of their physicochemical properties increased with increasing chain length of the nonionic emulsifier, but some of them followed a different trend for the two initiators. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1380–1384, 2005     

Effect of Copolymer Composition on the Dynamic Mechanical and Thermal Behaviour of Butyl Acrylate‐Acrylonitrile Copolymers

This article reports data on the dynamic mechanical and thermal behaviour of butyl acrylate‐acrylonitrile copolymers and their variation with copolymer composition. The copolymers were prepared by emulsion polymerisation techniques, using potassium peroxodisulfate initiator at 80 ± 2 °C. Films were prepared from the latex by casting and analysed by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). For copolymer with 0.7 weight fraction of butyl acrylate the dynamic mechanical behaviour was identical to the synthetic rubber NBR (acrylonitrile‐butadiene rubber), such that the storage modulus shows a rapid decay with increasing temperature. The damping characteristics, as indicated by the tan δ value, increased as the weight fraction of butyl acrylate in the copolymer increased. The dynamic mechanical data has been analysed with the WLF‐Equation to study the time‐temperature relationship. The dynamic mechanical properties and glass transition data point to the formation of a copolymer, whose properties vary with acrylonitrile content. Thermogravimetric analysis revealed that weight loss occurring at a particular temperature decreases, along with the decomposition rate, with increase in acrylonitrile content. The activation energy (E_a) for the decomposition was calculated using the Coats & Redfern equation. When temperatures for 10% copolymer decomposition are compared from TGA data, the acrylonitrile rich copolymer starts decomposing at a lower temperature, but the rate of decomposition is slower and yields higher char yields.

Effect of copolymer composition on the variation of tan δ (max) at a measuring frequency of 1 Hz.     

Mechanical and dynamic mechanical studies of resol/vinyl acetate‐2‐ethylhexylacrylate/ hexamethoxymethylmelamine interpenetrating network systems

Resol was solution blended with vinyl acetate–2‐ethylhexylacrylate (VAc–EHA) resin in aqueous medium, in varying weight fractions, with hexamethoxymethylmelamine (HMMM) as crosslinker, and data was compared with a control. The present work was aimed at getting an optimum combination of tensile strength, dynamic mechanical strength, impact strength, and toughness by synthesis of an interpenetrating network (IPN) of the resins. The control gave a semi‐IPN system, in which the resol crosslinked, while the acrylic did not, whereas the blend, where HMMM was the crosslinker, gave a full IPN system. Full IPNs of the resol/VAc–EHA system had higher moduli and ultimate tensile strength than the semi‐IPNs. Dynamic mechanical study showed that full IPN systems have higher T_g values than semi‐IPN systems. The impact strength increases with increasing proportions of VAc–EHA copolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1765–1771, 2003     

Acrylonitrile/vinyl acetate copolymer nanofibers with different vinylacetate content

In this study, free radical copolymerization of acrylonitrile (AN)–vinyl acetate (VAc) was performed for five different feed ratio of VAc (wt %) by using ammonium persulfate (APS) in the aqueous medium. The effect of VAc content on the spectrophotometric and thermal properties of AN–VAc copolymers was investigated by Fourier Transform Infrared–Attenuated Total Reflectance spectrophotometer (FTIR–ATR), differential scanning calorimeter (DSC), and thermal gravimetric analyzer (TGA). Thermal stability of homopolymer of AN is improved after being copolymerized. The electrospun P(AN‐co‐VAc) nanofibers were fabricated and the effect of VAc content on the morphologic properties of nanofibers was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The viscosity of the solution had a significant effect on P(AN‐co‐VAc) electrospinning and the nanofiber morphology. The average diameters of P(AN‐co‐VAc) nanofibers decreased 3.4 times with increasing feed ratio of VAc wt %. The P(AN‐co‐VAc) electrospun nanofiber mats, with the feed ratio of 30 wt % VAc, can be used as a nanofiber membrane in filtration and as a carbon nanofiber precursor for energy storage applications due to high surface to volume ratio, high thermal stability, homogeneous, and thinner nanofiber distribution. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Studies and characterization of RESOL/VAc–EHA/HMMM IPN systems in aqueous medium

Resol was solution‐blended with vinyl acetate‐2‐ethylhexyl acrylate (VAc–EHA) resin in an aqueous medium, in varying weight fractions, with hexamethoxymethylmelamine (HMMM) as a crosslinker and the data were compared with a control. The present work was aimed to obtain an optimum combination of high‐temperature resistance by synthesis of an interpenetrating network (IPN) of the resins. The control gave a semi‐IPN system, in which the resol crosslinked, while the acrylic did not, whereas the blend, where HMMM was the crosslinker, gave a full‐IPN system. FTIR spectra of the blends of resol/VAc–EHA/HMMM indicated the formation of new stretching, which was generated due to crosslinking reactions among VAc–EHA and the crosslinker HMMM. TGA showed that, with an increase in the VAc–EHA percent in semi‐IPNs, the decomposition temperature decreased gradually, whereas in case of full‐IPNs, the decomposition temperature increased with increase in the VAc–EHA percent. However, the full‐IPNs had a higher decomposition temperature than that of the semi‐IPNs, at the same resol/(VAc–EHA) ratio. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3581–3588, 2002     

Preparation of polystyrene/poly(vinyl acetate) nanocomposites with a core–shell structure via emulsifier‐free emulsion polymerization

Polystyrene/poly(vinyl acetate) latex nanoparticles with a core–shell morphology in an emulsifier‐free emulsion polymerization system were prepared with purified styrene and vinyl acetate (VAc) as monomers and 2,2′‐azo bis(2‐amino propane) dihydrochloride (ABA,2HCl) as the initiator and emulsifier. The optimized conditions of polymerization of VAc, on top of the already‐formed polystyrene as a core polymer, with a core–shell morphology were obtained using various parameters such as volume ratio of the first and second stages, type of process, and reaction time. The morphologic structure of the nanoparticles was studied by scanning electron microscopy and transmission electron microscopy. The latex nanoparticles and polymers were characterized by differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2409–2414, 2006     

New synthesis methods for polypropylene‐co‐ethylene‐propylene rubber

In this research, the reinforcement of polypropylene (PP) was studied using a new method that is more practical for synthesizing polypropylene‐block‐poly(ethylene‐propylene) copolymer (PP‐co‐EP), which can be used as a rubber toughening agent. This copolymer (PP‐co‐EP) could be synthesized by varying the feed condition and changing the feed gas in the batch reactor system using Ziegler–Natta catalysts system at a copolymerization temperature of 10°C. The ¹³C‐NMR tested by a 21.61‐ppm resonance peak indicated the incorporation of ethylene to propylene chains that could build up the microstructure of the block copolymer chain. Differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and dynamic mechanical analysis (DMA) results also confirmed these conclusions. Under these conditions, the morphology of copolymer trapped in PP matrix could be observed and the copolymer T_g would decrease when the amount of PP‐co‐EP was increased. DMA study also showed that PP‐co‐EP is good for the polypropylene reinforcement at low temperature. Moreover, the PP‐co‐EP content has an effect on the crystallinity and morphology of polymer blend, i.e., the crystallinity of polymer decreased when the PP‐co‐EP content increased, but tougher mechanical properties at low temperature were observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3609–3616, 2007     

Preparation of poly(styrene‐co‐butyl acrylate)/montmorillonite nanocomposite by emulsion polymerization: Characterization and nanoscratch behavior

Organic–inorganic hybrid poly(styrene‐co‐butyl acrylate)/organically modified montmorillonite (PSBA/organo‐MMT) latex particles have been prepared by in situ emulsion polymerization. The effects of modifier variety and the level of organo‐MMT have been investigated on the basis of the characteristics and mechanical properties of the resulting hybrid emulsion polymers. Although the more hydrophilic intercalated organic modifiers increased the latex particle size, the hydrophobic ones decreased the particle size. A more heterogeneous copolymer chain intercalation was seen by widespread XRD reflection as the organo‐MMT (organoclay) level increases. The tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were used to determine the dispersion state of organoclay particles inside the nanocomposite copolymer films. Dynamic mechanical thermal analysis (DMTA) showed that adding the organoclay to the copolymer decreased the maximum loss tangent (tanδ) value and caused the shift to a lower temperature. Interestingly, the incorporation of organoclay decreased the glass storage modulus of the copolymer, while increased the rubbery storage modulus to some extent. In addition, a standard indenter for the nanoscratching of copolymer nanocomposite films was used under low applied loads of 150 and 250 μN. The nanoscratch results showed that incorporation of a 3 wt % hydrophobic organoclay, e.g., Closite15A, in the copolymer matrix enhanced considerably the near‐surface hardness and grooving resistance of the nanocomposite film at room temperature. In fact, copolymer nanocomposite films with higher near‐surface hardness and tanδ curve broadening exhibited more nanoscratch resistance through a specific variety of viscoelastic deformation, which did not create a bigger groove. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of poly(butylene succinate)‐poly[2‐(dimethylamino)ethyl methacrylate] copolymers and their applications as carriers for drug delivery

Copolymers of poly[2‐(dimethylamino)ethyl methacrylate]–poly(butylene succinate)–poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA–PBS–PDMAEMA, PDBD) were synthesized through a chain‐extension reaction. The thermal properties characterized using differential scanning calorimetry showed that the introduction of PDMAEMA chains slightly decreased the melting temperature of PBS. The water contact angle of PDBD copolymer films with media of various pH decreased with a decrease of pH. This should be ascribed to the conformational transition of PDMAEMA blocks from a compact coil to an expanding shape in accordance with the variation of the pH of the surroundings. The results of dynamic light scattering and scanning electron microscopy revealed that PDBD copolymers could form spherical micelles with small particle size and narrow particle size distribution. Furthermore, drug loading (loading content, ca 10%; encapsulation efficiency, ca 60%) and release experiments were conducted using doxorubicin as a hydrophobic model drug. The results of release experiments of copolymer nanomicelles showed that these micelles had pH‐responsive properties. © 2018 Society of Chemical Industry     

Synthesis of styrene–maleic anhydride random copolymer and its compatibilization to poly(2,6‐dimethyl‐1,4‐phenylene ether)/brominated epoxy resin

Styrene–maleic anhydride random copolymer (R‐SMA_7.5), with a low content of maleic anhydride (MAH) of about 7.5 mol%, has been prepared, and the copolymer was characterized by fourier‐transform infrared (FTIR) and ¹³C NMR techniques showing that the product contained only random copolymer without blocks. The miscibility between poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE) and R‐SMA, was investigated by differential scanning calorimetry (DSC), showing that PPE was miscible with R‐SMA synthesized in our laboratory over the entire composition with low MAH content. A blend of R‐SMA₁₈ (MAH content is about 18 mol%) and PPE was also studied by DSC, which showed that PPE was immiscible when R‐SMA was the major component, although it was miscible with limited composition. FTIR investigation showed that R‐SMA could react with bromide epoxy (BEP) resin at high temperature (180°). The heat‐resistance and mechanical properties of R‐SMA/PPE/BEP systems were tested and analyzed, and results indicated that R‐SMA could improve the miscibility of PPE and BEP with increasing T_g of the BEP phase and decreasing the T_g of the PPE slightly, improving the breaking elongation and breaking energy, which resulted from good miscibility between PPE and BEP with R‐SMA as the compatibilizer. Finally, the properties of the composites (copper clad laminate) with R‐SMA_7.5 are studied and discussed. Copyright © 2003 Society of Chemical Industry     

Surface photocrosslinking of ethylene–vinyl acetate copolymer films

Surface photocrosslinking of ethylene–vinyl acetate (EVAc) copolymer films containing benzophenone (BP) was investigated for the purpose of replacing a poly(vinyl chloride) floor. The photogelatin in the EVAc films was effectively observed after UV radiation in the presence of oxygen. The crosslinking reaction was initiated from the surface of the irradiated film, which was mainly due to the dehydrogenation and generation of macroradicals of polymer by the light absorption of BP. The experiments of polyethylene–VAc with BP showed that the VAc‐rich amorphous part in the EVAc copolymer works as a crosslinking site. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1741–1745, 2000     

AB‐ and ABC‐type di‐ and triblock copolymers of poly[styrene‐block‐(ε‐caprolactone)] and poly[styrene‐block‐(ε‐caprolactone)‐block‐lactide]: synthesis,characterization and thermal studies

Polystyrene terminated with benzyl alcohol units was employed as a macroinitiator for ring‐opening polymerization of ε‐caprolactone and L ‐lactide to yield AB‐ and ABC‐type block copolymers. Even though there are many reports on the diblock copolymers of poly(styrene‐block‐lactide) and poly(styrene‐block‐lactone), this is the first report on the poly(styrene‐block‐lactone‐block‐lactide) triblock copolymer consisting of two semicrystalline and degradable segments. The triblock copolymers exhibited twin melting behavior in differential scanning calorimetry (DSC) analysis with thermal transitions corresponding to each of the lactone and lactide blocks. The block derived from ε‐caprolactone also showed crystallization transitions upon cooling from the melt. In the DSC analysis, one of the triblock copolymers showed an exothermic transition well above the melting temperature upon cooling. Thermogravimetric analysis of these block copolymers showed a two‐step degradation curve for the diblock copolymer and a three‐step degradation for the triblock copolymer with each of the degradation steps associated with each segment of the block copolymers. The present study shows that it is possible to make pure triblock copolymers with two semicrystalline segments which also consist of degradable blocks. Copyright © 2009 Society of Chemical Industry     

Studies on damping properties of P(MMA‐AN)/P(EA‐nBA) LIPNs

Using a two‐stage emulsion polymerization method, a series of poly(methyl methacrylate‐acrylonitrile)/poly(ethyl acrylate‐n‐butyl acrylate) [P(MMA‐AN)/P(EA‐nBA)] latex interpenetrating polymer networks (LIPNs) were synthesized by varying AN content, ratio of network I/network II, crosslinker content, and introducing chain transfer agent. The damping properties of the LIPNs were investigated using a Rheovibron Viscoelastometer. The results indicates that a suitable content of AN can improve the damping properties of the LIPNs. Three kinds of fillers were incorporated into the LPINs, respectively, to measure the change in the damping properties. Mica and TiO₂ both increased the damping properties of the LIPNs over the wide temperature range. For TiO₂‐filled LIPNs, it was observed that the tan δ values exceeded 0.4 over 112.6°C temperature range from −50 to 72.6°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 722–727, 2000     

Viscoelastic relaxation of styrene–butadiene–styrene block copolymers with different topological structures

The viscoelastic relaxation of linear styrene–butadiene–styrene triblock copolymer (l‐SBS) and star styrene–butadiene–styrene triblock copolymer (s‐SBS) with four arms were investigated with differential scanning calorimetry and dynamic rheological measurements. Three characteristic viscoelastic responses of l‐SBS and s‐SBS in the plot of the loss tangent (tan δ) and temperature at different frequencies (ω's), which corresponded to the relaxation of the polybutadiene (PB) block (peak I), the glass transition of the polystyrene (PS) phase (peak II), and the mutual diffusion between the PB blocks and PS blocks (peak III), respectively, were observed in the experimental range. Although ω was 0.1 rad/s, a noticeable peak III was gained for both l‐SBS and s‐SBS. The dynamic storage modulus (G′) of l‐SBS showed two distinct types of behavior, depending on the temperature. At temperature (T) < T₂ (where T₂ is the temperature corresponding to peak II), G′ of l‐SBS displayed a very weak ω dependency. In contrast, at T > T₂, G′ decayed much more rapidly. However, G′ of s‐SBS displayed a very weak ω dependency at both T < T₂ and T > T₂. Only near T₂ did s‐SBS decay with ω a little sharply. These indicated, in contrast to l‐SBS, that s‐SBS still exhibited more elasticity even at T > T₂ because of its crosslinking point between the PB blocks (the star structure). In the lower ω range, l‐SBS exhibited a stronger peak III than s‐SBS despite the same styrene content for l‐SBS and s‐SBS. The high tan δ value of peak III for l‐SBS was considered to be related to the internal friction among the PB blocks or the whole l‐SBS chain, not the PS blocks. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and morphology of a commercial high‐impact polypropylene in‐reactor alloy synthesized using a spherical Ziegler–Natta catalyst

A commercial high‐impact polypropylene (hiPP) was fractionated by temperature‐gradient elution fractionation into nine fractions. All fractions were studied using Fourier transform infrared spectroscopy and differential scanning calorimetry. The amount of ethylene in the fractions was also determined. The results demonstrate that the ethylene–propylene statistical copolymer (or ethylene–propylene rubber, EPR) content in this hiPP is rather low and the amounts of ethylene–propylene segmented copolymer and ethylene–propylene block copolymer (that act as adhesive and compatibilizer between elastomeric phase and matrix, respectively) are negligible. Furthermore, the morphology of the resin was studied using scanning electron microscopy observations of microtome‐cut original and etched samples, which reveals that EPR particles are too large and their distribution inside the matrix is not uniform. Copyright © 2010 Society of Chemical Industry     

Vibration control ability of multilayered composite material made of epoxy beam and polyurethane copolymer with shape memory effect

Sandwich‐type layered composite material was prepared with epoxy beam and polyurethane copolymer that was synthesized from 4,4‐methylene bis (phenylisocyanate), poly(tetramethyleneglycol), and 1,4‐butanediol as a chain extender. As for the polyurethane, shape recovery was improved with higher content of hard segment, and the highest damping effect as judged by tan δ was observed at 30–35% hard segment. The composite material had better impact strength and higher tan δ than epoxy beam alone, but the superiority became less as more hard segment was incorporated. The interfacial binding force between polyurethane and the epoxy beam also decreased in proportion to the hard segment content. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 302–307, 2004