Bulk modification of styrene–butadiene–styrene triblock copolymer with maleic anhydride

The bulk modification of SBS rubber with maleic anhydride in a mixing chamber of a Haake rheomixer was studied. The effect of temperature, maleic anhydride, and benzoyl peroxide concentrations on the grafting efficiency was evaluated. High grafting efficiency was achieved when the ratio of peroxide and maleic anhydride concentration was high. On the other hand, on this condition high insoluble fraction was generated. The addition of a diamine, 4,4′‐diaminediphenylmethane to the reaction mixture minimizes the amount of insoluble polymer. However, the grafted MAH content also decreases. The graft copolymer was characterized by infrared spectroscopy and the grafting extension was determined by titration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2953–2960, 2002; DOI 10.1002/app.10355     

Preparation of amphoteric latex by modification of styrene–acrylamide copolymer latex

Styrene–acrylamide copolymer latex prepared from the polymerization in an emulsifier-free aqueous medium was treated with hypochlorite and sodium hydroxide. The resulting latex indicated amphoteric property due to amino and carboxyl groups formed by the Hofmann reaction and competitive hydrolysis of amide groups, respectively. Amphoteric latices with the same particle size but different charge density (1.0–3.0 ionic groups/100 Ų) and different isoelectric points (6.4–9.2) have been prepared by changing the reaction conditions.     

Dynamic mechanical properties of short carbon fiber-filled styrene–isoprene–styrene block copolymer

The mechanical and dynamic mechanical properties of short carbon fiber-filled styrene–isoprene–styrene (S–I–S) block thermoplastic elastomeric composite have been studied. Brabender mixing followed by milling of the fiber–rubber compositions caused about a 30-fold decrease in the fiber aspect ratio and random fiber orientation. Although low-strain moduli increased on fiber incorporation, tensile and tear properties dropped and anisotropy in mechanical properties was not observed. Tan δ values at the T_g region decreased on filler incorporation, but at room temperature, the tan δ values increased with filler loading. The variation of storage moduli and tan δ values with frequency followed a pattern similar to the variation of these properties with filler incorporation. © 1993 John Wiley & Sons, Inc.     

Preparation and performance in paper coating of silicone‐modified styrene–butyl acrylate copolymer latex

Silicone‐modified styrene–butyl acrylate copolymer latex was synthesized by emulsion copolymerization by using octamethylcyclotetrasiloxane (D₄), styrene, and butyl acrylate as raw materials, potassium persulfate as initiator and propylmethacrylate triethoxysilane (KH‐570) as crosslinking agent. The infrared spectra studies showed that the vinyl monomers were completely copolymerized with D₄. The prepared silicone‐modified copolymer latex with the interpenetrating polymer networks tended to have higher stability, and better toluene and water resistance than styrene–butyl acrylate latex. The glossiness of coated paper was improved with silicone‐modified copolymer latex, and it was at a maximum when D₄ was about 3% of total monomers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 333–336, 2001     

The influence of styrene–butadiene diblock copolymer on styrene–butadiene–styrene triblock copolymer viscoelastic properties and product performance

The effects of the styrene–butadiene (SB) diblock copolymer on the viscoelastic properties of styrene–butadiene–styrene (SBS) triblock copolymers were examined in both in the the neat state and within specific product applications. The addition of the SB diblock copolymer into a pure SBS triblock copolymer resulted in a significant decrease in the plateau storage modulus and a quantitative linear rise in tan delta. In a pure triblock, in which all endblocks are anchored in polystyrene domains, all entanglements are physically trapped. The SB diblock embodies untrapped polybutadiene endblocks that are able to relax stress by chain reptation through the rubbery polybutadiene matrix. The SB diblock copolymer quantitatively lowered the microphase separation temperature (MST) of the SBS triblock copolymer. These changes in linear viscoelastic behavior manifest themselves into a reduction in the efficiency and performance of the SBS triblock copolymer in asphalt pavement binders and hot-melt adhesive blends. Specifically, the SB diblock diminished the complex shear modulus and elasticity of a polymer-modified asphalt, which translated into lower predicted rutting specification values. The increase in diblock content altered the viscoelastic response of the hot-melt adhesive blend, translating into a reduction in the shear holding power and shear adhesion failure temperature. The lack of network participation, coupled with the relaxation of the polybutadiene endblocks, accounts for the lower strength and greater temperature susceptibility of the diblock-containing systems. © 1995 John Wiley & Sons, Inc.     

Electromagnetic interference properties of carbon nanofiber–reinforced acrylonitrile–styrene–acrylate/natural graphite composites

Acrylonitrile–styrene–acrylate/natural graphite/carbon nanofiber composites (ASA/NG/CNF) were prepared using a melting blending method. The effects of CNFs on the morphology, rheological properties, dynamical mechanical properties, electrical resistivity, and electromagnetic interference shielding effectiveness (EMI SE) were studied using a scanning electron microscope, a rotational rheometer, and dynamic mechanical analysis (DMA). The addition of CNFs changed the oriented and laminated structure of the ASA/NG composite. The flexural strength of the ASA composite reached a maximum at 6% CNF, and then it began to decrease. The addition of CNFs did not alter the glass‐transition temperature of ASA, but it largely increased the storage modulus of the composite in DMA tests. In the rheological measurements, the complex viscosity and storage modulus of the composite increased as CNF content increased, and the resistance to creep of the composites was significantly increased by the addition of CNFs. The electrical resistivity of the ASA composites decreased from 49.8 Ω cm to 2.3 Ω cm as the CNF content was increased from 0 to 12%. At the same time, the EMI properties of the composites rose from 15 dB to 30 dB in the frequency range 30–1500 MHz. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45455.     

Degradation mechanism of styrene–polyester copolymer

The degradation mechanism of styrene–polyester copolymer was studied by various experimental techniques such as TGA, DTA, IR spectroscopy, pyrolysis gas chromatography, and GCMS (gas chromatography–mass spectrometry). It is concluded that, mainly, there are two first-order degradation reactions during thermal degradation in the presence of air. The first step involves the scission of crosslinks/weak links with liberation of free linear chains. The second degradation step involves random scission of the free linear chains into smaller fragments. The various fragments were identified by pyrolysis gas chromatography and by GCMS. In oxygen atmosphere, the polymer was found to obey first-order kinetics with a single rate constant. Apparently, due to presence of oxygen species at the degrading surface, the two rate constants obtained during thermal degradation reaction are altered in such a fashion as to give a single rate constant.     

Porous maleic anhydride–styrene–divinylbenzene copolymer beads

The formation of the porosity and the pore stability in maleic anhydride–styrene–divinylbenzene (MAn–St–DVB) copolymer beads were investigated using the apparent density measurements of the samples dried from methanol (maximum porosity) and from dioxane (stable porosity). The copolymer beads were prepared by the suspension polymerization method in glycerol instead of water as the dispersing medium. A toluene–dioxane (1:1) mixture was used as the diluent at a fixed volume fraction of the organic phase (0.47). Compared to St–DVB copolymers prepared in the presence of nonsolvating diluents, porous MAn–St–DVB copolymers are obtained at relatively low DVB concentration, i.e., at 1–3% DVB. The porosity of the copolymers increases with decreasing MAn concentration in the feed due to the decrease in the copolymer yield. The results of the elemental analyses and titrimetric methods indicate that approximately only half of the MAn units in the copolymer are able to react with amine or with water. A possible rearrangement of the MAn units into the cyclopentanone structures was suggested.     

Compositional analysis of the styrene–isobutylene copolymer

Analysis for composition of the styrene–isobutylene copolymer has been accomplished by independent techniques which include carbon-hydrogen analysis and infrared and NMR spectroscopy. The use of blends of homopolymers presents difficulties in establishing true absorptivities for the solution of two-component systems, and appropriate corrections were applied to enable use of IR as an analytical technique. Carbonhydrogen elemental analysis and NMR spectroscopy were used to verify the IR results.     

Dichlorocarbene modification of styrene–butadiene rubber

Dichlorocarbene-modified styrene–butadiene rubber (SBR) prepared by the alkaline hydrolysis of chloroform using cetyltrimethylammonium bromide as a phase-transfer agent resulted in a product that showed good mechanical properties, excellent flame resistance, solvent resistance, and good thermal stability. The activation energy for this chemical reaction calculated from the time–temperature data on the chemical reaction by the measurement of the percentage of chlorine indicated that the reaction proceeded according to first-order kinetics. The molecular weight of the polymers, determined by gel permeation chromatography, showed that chemical modification was accompanied by an increase in molecular weight. The chemical modification was characterized by proton NMR, FTIR studies, thermogravimetric analysis, and flammability measurement. Proton NMR and FTIR studies revealed the attachment of chlorine through cyclopropyl rings to the double bond of butadiene. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 153–160, 1998     

Thermal behaviors and flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives

The thermal behaviors and the flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives were studied. The combustion was measured by the Underwriter laboratory (UL) test and cone calorimeter test and thermogravimetric analysis and program‐mass spectroscopy were applied to analyze the thermal behaviors. The blend with halogen additives showed the best result in the UL test. However, the blend with red‐phosphorous was the best in the cone calorimeter test. As the styrene sequence in the copolymer tended to degradate at a lower temperature, the major scission products spouted out from the polymer surface originated from polystyrene. The shorter the ignition times of the blends with red‐phosphorous were, the lower the peak heat release rates were. It was an interesting phenomenon because it suggested that the chemical structure of the residue changed to more stable polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 156–161, 2007     

Preparation and properties of styrene–ethylene–butylene–styrene block copolymer/clay nanocomposites: I. Effect of clay content and compatibilizer types

BACKGROUND: Polymer/clay (silicate) systems exhibit great promise for industrial applications due to their ability to display synergistically advanced properties with relatively small amounts of clay loads. The effects of various compatibilizers on styrene–ethylene–butylene–styrene block copolymer (SEBS)/clay nanocomposites with various amounts of clay using a melt mixing process are investigated. RESULTS: SEBS/clay nanocomposites were prepared via melt mixing. Two types of maleated compatibilizers, styrene–ethylene–butylene–styrene block copolymer grafted maleic anhydride (SEBS‐g‐MA) and polypropylene grafted maleic anhydride (PP‐g‐MA), were incorporated to improve the dispersion of various amounts of commercial organoclay (denoted as 20A). Experimental samples were analyzed using X‐ray diffraction and transmission electron microscopy. Thermal stability was enhanced through the addition of clay with or without compatibilizers. The dynamic mechanical properties and rheological properties indicated enhanced interaction for the compatibilized nanocomposites. In particular, the PP‐g‐MA compatibilized system conferred higher tensile strength or Young's modulus than the SEBS‐g‐MA compatibilized system, although SEBS‐g‐MA seemed to further expand the interlayer spacing of the clay compared with PP‐g‐MA. CONCLUSION: These unusual results suggest that the matrix properties and compatibilizer types are crucial factors in attaining the best mechanical property performance at a specific clay content. Copyright © 2007 Society of Chemical Industry     

Nano-indentation for probing mechanical properties of nanocomposites based on ethylene butyl acrylate copolymer and carbon black

Mechanical properties of heterogeneous systems based on carbon black (CB) filled semi-crystalline ethylene butyl acrylate (EBA) copolymer nanocomposites are characterized using nano-indentation technique. The size effect and CB content dependence on the deformation behavior at room temperature were investigated. The phenomenology for hardness response (H) indicates a typical enhancement of the H when the indentation depth (h) decreases as for the usual elastomeric materials. All H–h curves, fitted according to the Meyer's empirical power law and Franck elasticity model, highlight the so-called length-scale-dependent deformation. Similar trend is observed for the elastic modulus. Furthermore, it is evidenced that the increases of CB content increases the mechanical properties of composites, that is, hardness and elastic modulus. This behavior can be mainly related, on the one hand, to the change of the meso-structure, formed by the interconnected network of polymer and the aggregates of CB particles and to the nature of the polymer matrix, on the other hand. The mechanical properties characterized from micro and submicron indentations were compared to that characterized at macroscopic scale to highlight the possible correlations between the two scales. This investigation can interest many applications of polymer composites for rubber technology such as tires industry, soft robotic, and adhesives. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47897.     

Preparation and characterisation of styrene—methyl methacrylate and styrene–methacrylic acid copolymer latices

Series of styrene-methyl methacrylate and styrene-methacrylic acid copolymer latices have been prepared by emulsion polymerisation using polyoxyethylene nonyl phenyl ether as emulsifier and potassium persulphate as initiator. the effects of surfactant concentration and monomer composition on the ultimate particle size and conversion were investigated. The ultimate particle diameters decreased with increasing surfactant concentration, while the conversions were found to be almost independent of surfactant concentration. The ultimate particle diameters were notably decreased by increasing the content of methacrylic acid. Trace carboxyl groups were detected both in polystyrene latex and styrene-methyl methacrylate copolymer latices. The number of sulphate groups on the polystyrene latex surface was about five times that of carboxyl groups.     

Vibration damping and electrical conductivity of styrene–butyl acrylate random copolymers filled with carbon black

Emulsion‐polymerized poly(styrene‐rand‐butyl acrylate) (St–BA) copolymers exhibit damping capabilities over a wide temperature range with changes in the monomer ratio. Blending copolymers of different compositions results in a multidamping peak, further widening the effective damping temperature range. Adding carbon black (CB) reduces the peak damping intensity but enhances damping at higher temperatures. The addition of dodecyl benzene sulfonic acid to an St–BA/CB aqueous dispersion improves the dispersion of CB in the polymer, reducing the percolation threshold and improving the conductivity while slightly affecting the mechanical behavior. The electrical properties of the St–BA/CB system are affected by the copolymer composition, influencing the polymer surface tension. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Amphiphilic styrene–butadiene–styrene triblock copolymer grafted with polyoxyethylene

A styrene–butadiene–styrene triblock copolymer (SBS) was grafted with polyoxyethylene via a ring‐opening reaction of an epoxidized styrene–butadiene– styrene triblock copolymer (ESBS) with monocarboxylic‐group‐terminated methoxypoly(ethylene glycol) (CMPEG). The latter was prepared through the esterification of methoxypoly(ethylene glycol) with maleic anhydride. The optimum conditions for the preparation of the graft copolymer were studied. The graft copolymer was characterized with Fourier transform infrared spectrophotometry. Its water absorbency, oil absorbency, emulsifying property, phase‐transfer catalysis property in the Williamson solid–liquid reaction, and use as a compatibilizer in the blending of SBS with oil‐resistant chlorohydrin rubber (CHR) were also studied. The optimum conditions were a CMPEG/epoxy group molar ratio of 1.5, an N,N‐dimethyl aniline/ESBS concentration of 5 wt %, and an ESBS concentration of 12–14 g/100 mL at 75–80°C for 10 h. The polyoxyethylene content could reach 0.27 mmol/g. The graft copolymer absorbed a certain amount of water, fairly resisted kerosene, and possessed good emulsifying and phase‐transfer catalysis properties, both of which were enhanced with increasing polyoxyethylene graft content. The graft copolymer could be used as a compatibilizer for a blend of SBS and CHR. A 3 wt % concentration of the graft copolymer based on a 50/50 blend could increase both the tensile strength and ultimate elongation of the blend about 1.7 times. The blend behaved like an oil‐resistant thermoplastic elastomer. Scanning electron microscopy demonstrated the improved compatibility of the two components by the graft copolymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of styrene–divinylbenzene copolymer by anchoring ferric–dipyridylamine complex

Polystyrene–divinylbenzene (PS–DVB) copolymer was modified by anchoring dipyridylamine (DPA) on it followed by complexation with Fe(III). Under the experimental conditions followed, 9% incorporation of Fe(III) was achieved. PS–DVB–DPA and PS–DVB–DPA–Fe(III) were characterized by IR spectra. Diffuse reflectance spectra for PS–DVB–DPA–Fe(III) and DPA–Fe(III) revealed λ_max at ～ 360 and ～ 310, respectively. This difference could be due to a difference in the nature of the coordinating moieties complexing with Fe(III) in these two systems. Scanning electron micrographs of PS–DVB, PS–DVB–DPA–Fe(III), and heat-treated PS–DVB–DPA–Fe(III) revealed some typical surface features. Thermal stability varied in the order PS–DVB–DPA–Fe(III) > PS–DVB–DPA ?PS–DVB, and DTA showed characteristic exotherms. © 1992 John Wiley & Sons, Inc.     

Influence of addition of styrene–ethylene/butylene–styrene copolymer on rheological,mechanical, and tribological properties of polyamide nanocomposites

To develop new tribomaterials for mechanical sliding parts, investigations were carried out on the influence of adding styrene–ethylene/butylene–styrene block copolymer (SEBS) on the rheological, mechanical, and tribological properties of polyamide 6 (PA6) nanocomposite, which is a commercial product of layered silicate (clay) filled polyamide 6 (PA6/Clay). Two kinds of block copolymers, unmodified SEBS (SEBS) and maleic anhydride‐grafted SEBS (SEBS‐g‐MA), were added with PA6/Clay nanocomposite. Dynamic viscoelastic properties in the molten state of these nanocomposites and their tensile, impact, and tribological properties of these nanocomposites were evaluated. Dynamic viscoelastic properties were found to increase with the addition of SEBS and were influenced, in particular, by block copolymers containing SEBS‐g‐MA. Influence of the addition of SEBS on mechanical properties of these systems differed for each mechanical property. Although tensile properties decreased with SEBS, Izod impact properties were improved with the addition of SEBS‐g‐MA. Tribological properties were improved with the addition of block copolymer, and the influence of the amount of addition was higher than the type of block copolymer used. These results indicate that new tribomaterials developed have sufficient balance amongst moldability, mechanical, and tribological properties. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers