Effect of organoclay and silver‐substituted zeolite on the mechanical and antibacterial properties of a silicone rubber filled with 2‐hydroxypropyl‐3‐piperazinyl‐quinoline carboxylic acid methacrylate

Silicone rubber compounds filled with different loadings of organoclay (OC) and silver substituted zeolite (SSZ) solid fillers were prepared and cured with 2,5‐dimethyl‐2,5‐di(tert‐butylperoxy) hexane. The rubber vulcanizates contained an antimicrobial agent to protect them against Escherichia coli (E. coli ATCC 25922) and Staphylococcus aureus (S. aureus ATCC 25923) bacteria. The tensile strength, elongation at break, stored energy density at break, Young's modulus, modulus at 100% elongation, cyclic fatigue life, and glass transition temperature of the rubber vulcanizates were subsequently measured. The antimicrobial performance of the rubber surfaces were determined by disk diffusion testing and plate count agar method. The antimicrobial agent had an adverse effect on the mechanical properties, but the cyclic fatigue life of the rubber vulcanizate improved. The addition of OC and SSZ could improve the tensile strength, elongation at break and stored energy density at break, but deteriorated the tear energy, Young's modulus and modulus at 100% elongation. The inclusion of the fillers was not beneficial to the antimicrobial activity of the rubber against bacteria. The HPQM in the rubber was effective more against E. coli. than against S. aureus. Furthermore, the antimicrobial activity increased when the contact time in the test solution was increased. POLYM. ENG. SCI., 54:932–941, 2014. © 2013 Society of Plastics Engineers     

Cure retardation of peroxide‐cured silica filled natural rubber influenced by organosilane

The influence of silane coupling agent on properties of silica‐filled compounds under peroxide curing was investigated. bis (triethoxysilylpropyl) tetrasulfide (TESPT) was selected in this study and its content was varied from 0 to 12% w/w of silica. It is found that with increasing TESPT content, bound rubber content, tensile strength, elongation at break and tear strength are enhanced. By contrast, magnitude of Payne's effect, modulus at 100% elongation (M₁₀₀) and heat build‐up are decreased. The changes of such properties are attributed to the reduction of crosslink density in conjunction with the improvements of both rubber–filler interaction and degree of filler dispersion with increasing TESPT content in the peroxide curing system. POLYM. ENG. SCI., 59:42–48, 2019. © 2018 Society of Plastics Engineers     

Reinforcement of peroxide‐cured styrene–butadiene rubber vulcanizates by mathacrylic acid and magnesium oxide

Through the neutralization of magnesium oxide (MgO) and methacrylic acid (MAA), magnesium methacrylate [Mg(MAA)₂] was in situ prepared in styrene–butadiene rubber (SBR) and used to reinforce the SBR vulcanizates cured by dicumyl peroxide (DCP). The experimental results show that the mechanical properties, dynamic mechanical properties, optical properties, and crosslink structure of the Mg(MAA)₂‐reinforced SBR vulcanizates depend on the DCP content, Mg(MAA)₂ content, and the mole ratio of MgO/MAA. The formulation containing DCP 0.6–0.9 phr, Mg(MAA)₂ 30–40 phr, and MgO/MAA mole ratio 0.50–0.75 is recommended for good mechanical properties of the SBR vulcanizates. The tensile strength of the SBR vulcanizates is up to 31.4 MPa when the DCP content is 0.6 phr and the Mg(MAA)₂ content is 30 phr. The SBR vulcanizate have good aging resistance and limited retention of tensile strength at 100°C. The SBR vulcanizates are semitransparent, and have a good combination of high hardness, high tensile strength, and elongation at break. The T_g values of the SBR vulcanizates depend largely on the DCP content, but depend less on the Mg(MAA)₂ content and the MgO/MAA mole ratio. The contents of DCP, Mg(MAA)₂, and the MgO/MAA mole ratio have also great effects on the E′ values of the vulcanizates. The salt crosslink density is greatly affected by the Mg(MAA)₂ content and MgO/MAA mole ratio, but less affected by the DCP content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2667–2676, 2002     

Preparation of antimicrobial poly(ϵ‐caprolactone) electrospun nanofibers containing silver‐loaded zirconium phosphate nanoparticles

Antimicrobial nanofibers of poly(?‐caprolactone) (PCL) were prepared by electrospinning of a PCL solution with small amounts of silver‐loaded zirconium phosphate nanoparticles (nanoAgZ) for potential use in wound dressing applications. The electrospun nanoAgZ‐containing PCL nanofibers were characterized using field emission scanning electron microscopy, energy dispersive X‐ray spectrum (EDX), X‐ray diffraction analysis (XRD), antimicrobial tests, and biocompatibility tests. The SEM, EDX, and XRD investigations of the electrospun fibers confirmed that silver‐containing nanoparticles were incorporated and well dispersed in smooth and beadless PCL nanofibers. The results of the antimicrobial tests showed that these fibers have maintained the strong killing abilities of Ag⁺ existed in the nanoAgZ against the tested bacteria strains and discoloration has not been observed for the nanofibers. To test the biocompatibility of nanofibers as potential wound dressings, primary human dermal fibroblasts (HDFs) were cultured on the nanofibrous mats. The cultured cells were evaluated in terms of cell proliferation and morphology. The results indicated that the cells attached and proliferated as continuous layers on the nanoAgZ‐containing nanofibers and maintained the healthy morphology of HDFs. The earlier results suggested that nanoAgZ‐containing fibers may be expected to be a novel material for potential wound dressing applications because of the significant bacteriostatic activities and good biocompatibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Cure characteristics and physical properties of ground‐rubber‐filled natural rubber vulcanizates: Effects of the curing systems of the ground rubber and rubber matrix

Recycling discarded rubber is important for both environmental and economic reasons. One of the most attractive methods of recycling rubber waste is to use ground rubber (GR) as a compounding ingredient or as a replacement for raw polymers. In this study, ground natural rubber was prepared with different curing systems and compounded into the parent compounds. The cure behaviors and physical properties of the GR‐filled vulcanizates were investigated, and they were largely affected by the curing systems of the rubber matrix and GR. GR‐filled vulcanizates with GR and the rubber matrix, having a conventional curing system, showed the largest changes in the cure characteristics. The greatest decrease in the physical properties was observed for peroxide‐cured‐GR‐filled vulcanizates. The addition of GR decreased the crosslink density of the GR‐filled vulcanizates. This was thought to be the main reason for the reduction of the mechanical properties of the GR‐filled vulcanizates. However, the adhesion between the GR and rubber matrix may also have caused the differences in the physical properties of the GR‐filled vulcanizates with respect to the curing systems of the rubber matrix and GR. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Study on the optical properties of sulfur‐containing poly(methyl methacrylate)‐inorganic hybrid

High refractive index homogeneous hybrid materials were successfully prepared. The polymer matrix was the copolymer of methyl methacrylate, sulfur‐containing monomer 2,2′‐mercaptoethylsulfide dimethacrylate (MESDMA), and nanotitania was prepared by in situ solgel process of titanium n‐butoxide. The transmission electron microscope (TEM) study suggested that the hybrid was homogeneous without inorganic agglomerate, and the inorganic particles were 4–7 nm. The refractive index was ～ 1.75 when the inorganic content of the hybrid film reached to 70 wt %, and the transmittance maintained up to 85%. The sulfur‐containing monomer was used to improve the refractive index, also, it was a crosslinking reagent, which improved the film‐forming ability of the hybrid. After copolymerized with MESDMA, the film‐forming ability of the hybrid was better than the one without MESDMA. Even if the inorganic content exceeded 75 wt %, the films kept integrity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Using hydroxypropyl‐β‐cyclodextrin for the preparation of hydrophobic poly(ketoethyl methacrylate) in aqueous medium

This work was committed to the polymerization of hydrophobic ketoethyl methacrylate monomer in aqueous medium in the presence of cyclodextrin, instead of polymerizing the monomer in toxic and volatile organic solvents. For this purpose, a new ketoethyl methacrylate monomer, p‐methylphenacylmethacrylate (MPMA), was synthesized from the reaction of p‐methylphenacylbromide with sodium methacrylate in the presence of triethylbenzylammonium chloride. The monomer was identified with FTIR, ¹H and ¹³C‐NMR spectroscopies. Hydroxypropyl‐β‐cyclodextrin (HPCD) was used to form a water‐soluble host/guest inclusion complex (MPMA/HPCD) with the hydrophobic monomer. The complex was identified with FTIR and NMR techniques and polymerized in aqueous medium using potassium persulfate as initiator. During polymerization the resulting hydrophobic methacrylate polymer precipitated out with a majority of HPCD left in solution and a minority of HPCD bonded on the resulting polymer. The thus‐prepared polymer exhibited little difference from the counterparts obtained in organic solvent in number average molecular weight (M_n), polydispersity (M_w/M_n) and yield. The investigation provides a novel strategy for preparing hydrophobic ketoethyl methacrylate polymer in aqueous medium by using a monomer/HPCD inclusion complex. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Properties of vulcanizates from blends of natural rubber and thioglycolic acid modified,epoxidized, low‐molecular‐weight natural rubber filled with carbonized rubber seed shell

Vulcanizates from blends of natural rubber and thioglycolic acid modified, epoxidized, low‐molecular‐weight natural rubber filled with mixtures of carbon black and carbonized rubber seed shell, with semiefficient sulfur vulcanization recipes, were critically investigated and characterized. The investigated properties were the processing and rheological properties (the cure rate, cure time, scorch time, total oscillating disc rheometry torque, and Mooney viscosity), physicomechanical and chemical properties, solvent resistance, solubility, and swelling properties. On the basis of the investigated properties, it was observed that the carbonized rubber seed shell acted as a plasticizer and not as a reinforcing filler such as carbon black. The replacement of carbon black with up to 20% carbonized rubber seed shell produced vulcanizates having processing advantages in time gain and energy consumption, with their physical, chemical, and mechanical properties around the acceptable level for natural rubber compounds but lower than the properties obtained for a 100% carbon black filled vulcanizate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Scratch behavior of epoxy nanocomposites containing α‐zirconium phosphate and core‐shell rubber particles

The effects of nanoscale core‐shell rubber (CSR) particles and α‐zirconium phosphate (ZrP) nanoplatelet fillers on the scratch behavior of epoxy have been examined using a newly established ASTM scratch testing method. The critical load for onset of microcrack formation is utilized to determine scratch resistance of the epoxy nanocomposites. Optical microscopy and scanning electron microscopy were performed to determine failure and fracture patterns caused by the scratch. The findings of this study suggest that the introduction of nanoparticles or nanoplatelets does not necessarily enhance the scratch resistance of epoxy. This implies that increases in ductility and fracture toughness alone, i.e., the epoxy/CSR case, and enhancements in modulus and tensile strength alone, i.e., the epoxy/ZrP case, will not necessarily improve scratch resistance of epoxy matrix. A combination of material property attributes is needed to prepare scratch resistant polymers. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

4‐chloro‐3‐methylphenyl methacrylate copolymers with 2,4‐dichlorophenyl methacrylate: Synthesis,characterization, and antimicrobial activity

4‐Chloro‐3‐methylphenyl methacrylate (CMPM) and 2,4‐dichlorophenyl methacrylate (2,4‐DMA) were synthesized by reacting methacryloyl chloride with 4‐chloro‐3‐methylphenol (CMP) and 2,4‐dichlorophenol (2,4‐DP), respectively. Homo and copolymers of CMPM and 2,4‐DMA were obtained from different monomer feed ratios, using 2,2′‐azobisisobutyronitrile as initiator in toluene at 70°C. IR‐spectroscopy was employed to characterize the resulting homo and copolymers. Copolymer compositions were determined by ultraviolet (UV) spectroscopy. Fineman–Ross method was used to calculate the reactivity ratios of the monomers. Average molecular weight and polydispersity index were obtained by gel permeation chromatography (GPC). Thermogravimetric analyses (TGA) and differential thermal analysis (DTA) of copolymers were carried out under a nitrogen atmosphere. Antimicrobial effects of the homo and copolymers were also investigated for various microorganisms such as bacteria, fungi, and yeast. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:439–448, 2006     

Infrared spectroscopic studies of poly(methyl methacrylate) doped with a new sulfur‐containing ligand and its cobalt(II) complex during γ‐radiolysis

Infrared (IR) spectroscopy studies were performed for poly(methyl methacrylate) (PMMA) samples doped with an organic ligand or its cobalt(II) complex after the extraction of the dopant during γ‐radiolysis. There were no drastic changes in the IR absorption band position, but noticeable changes in the intensities were found. The relative transmission of IR absorption bands, such as those at 750, 840, 1065, and 1388 cm^?1, were measured according to the transmission of the carbonyl group band at 1717 cm^?1. The degradation and recombination mechanism of different groups in the polymeric chain or backbone during radiolysis could be explained by the behavior of the relative transmission data for each group with increasing exposure dose. The tacticity of the PMMA samples was unchanged during radiolysis, and they were found to be syndiotactic. This was confirmed by the IR J values for different PMMA samples before and after irradiation. The protection efficiency of the organic ligand and its cobalt(II) complex was also investigated, and it was found that the organic ligand was more protective than the cobalt(II) complex for PMMA samples against γ‐rays. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1937–1950, 2004     

Crack growth and abrasion resistance of carbon black‐filled purified natural rubber vulcanizates

The influence of parameters contributing to rubber stiffness, including, crosslink density, hardness, and modulus, on the crack growth and abrasion resistance of carbon black‐filled purified natural rubber (PNR) vulcanizates as well as a whole natural rubber (WNR) vulcanizate counterpart or a control were elucidated. In addition, the tensile properties of PNR and WNR were also determined. PNR containing the same curative level as that of the control had lower stiffness and exhibited superior crack growth resistance. The results revealed that the improved crack growth resistance of PNR, compared to the control, was due to its lower crosslink density, hardness, and modulus. In addition, the tensile strength and abrasion resistance of PNR vulcanizates were not as sensitive as the crack growth resistance to the changes of their stiffness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1793–1796, 2003     

Strain‐induced crystallization behavior of natural rubber and trans‐1,4‐polyisoprene crosslinked blends

The strain‐induced crystallization (SIC) behaviors of crosslinked blends based on natural rubber (NR) and trans‐1,4‐polyisoprene (TPI) with different content of TPI were probed explored by using synchrotron two‐dimensional wide angle X‐ray diffraction and dynamic mechanical analysis. The results showed that when TPI content is less than 70% no reflection peak of TPI but NR crystallite diffractions can be observed and the diffractions of TPI βform appear when TPI content is 70 wt % in the cocured blend. SIC of cocured blends started at smaller strain ratio than the pure NR. By calculating ΔS_def, it is found that the drop in entropy upon strain decreased when TPI is incorporated into NR due to the reduction of molecular mobility of NR. The degree of SIC and crystallization rate index in crosslinked blends monotonously decreased with the increase of TPI content. The apparent crystallite size exhibited some surprising variations. L₂₀₀ and L₁₂₀ decreased with the increase of TPI content in the cocured blends. These observations were usually caused by two factors: (i) Less number of polymer chains could involve in crystal growth due to the lower mobility of polymer chains in the cocured blends which is proved by dynamic mechanical analysis results; (ii) The mean distance between nuclei decreases, which was caused by the fluctuation of crosslink density in NR phase derived from the heterogeneous distribution of curatives in two phases supported by the varying tendency of curing degree and crosslink density. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and coordination with Hg(II) of sulfur‐ and 2‐amino‐pyridine‐containing chelating resin

A novel chelating resin anchoring 2‐amino‐pyridine on macroporous crosslinked polystyrene beads via a sulfur‐containing spacer (PVBS‐AP) has been synthesized and its structures were characterized by FTIR, scanning electron microscopy, porous structure analysis, and elementary analysis. The results of scanning electron microscopy and pores analysis demonstrated that PVBS‐AP resin had meso‐macro porous structure. Its adsorption properties for Hg(II), Pd(II), Ni(II), Cu(II), Zn(II), Pb(II), and Cd(II) were investigated. Some factors affecting the adsorption of PVBS‐AP resin for Hg(II), such as temperature, contact time, ion concentration, and pH were also studied. The results showed that the increasing of temperature was beneficial to adsorption and Langmuir model was much better than Freundlich model to describe the isothermal process. PVBS‐AP resin had good adsorption selectivity for Hg(II). It could selective adsorb Hg(II) from such binary ions system as Hg(II)‐Ni(II), Hg(II)‐Zn(II), and Hg(II)‐Pb(II), their selective coefficients are α_Hg/Ni = ∞, α_Hg/Zn = 28.1, α_Hg/Pb = ∞, respectively. Five adsorption–desorption cycles demonstrate that this resin were suitable for reuse without considerable change in adsorption capacity. POLYM. ENG. SCI., 47:721–727, 2007. © 2007 Society of Plastics Engineers.     

Stress‐relaxation behavior of natural rubber/polystyrene and natural rubber/polystyrene/natural rubber‐graft‐polystyrene blends

We studied the stress‐relaxation behavior of natural rubber (NR)/polystyrene (PS) blends in tension. The effects of strain level, composition, compatibilizer loading, and aging on the stress‐relaxation behavior were investigated in detail. The dispersed/matrix phase morphology always showed a two‐stage mechanism. On the other hand, the cocontinuos morphology showed a single‐stage mechanism. The addition of a compatibilizer (NR‐g‐PS) into 50/50 blends changed the blend morphology to a matrix/dispersed phase structure. As a result, a two‐step relaxation mechanism was found in the compatibilized blends. A three‐stage mechanism was observed at very high loadings of the compatibilizer (above the critical micelle concentration), where the compatibilizer formed micelles in the continuous phase. The aged samples showed a two‐stage relaxation mechanism. The rate of relaxation increased with strain levels. The aging produced interesting effects on the relaxation pattern. The rate of relaxation increased with temperature due to the degradation of the samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Swelling behavior of pH‐ and temperature‐sensitive copolymers containing 2‐hydroxy‐ethyl methacrylate and N‐vinyl‐2‐pyrrolidone crosslinked with new crosslinkers

Copolymers of 2‐hydroxyethyl methacrylate (HEMA) and N‐vinyl‐2‐pyrrolidone (VP) and homopolymers of HEMA and VP were crosslinked in the presence of different mol% of melamine trimethacrylamide (MMAm) and melamine triacrylamide (MAAm) as crosslinkers by bulk radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Lower critical solution transition temperatures (LCST) were measured by DSC. The properties of crosslinked HEMA and VP copolymers, VP and HEMA series were evaluated in terms of compositional drift of polymerization, heterogeneous crosslinking, and chemical structure of the relevant components. Soluble fractions of the crosslinked networks were reduced by varying the MAAm and MMAm concentrations. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. This behavior is explained on the basis that amide groups of VP or crosslinkers could be hydrolyzed to form negatively charged carboxylate ion groups in the produced networks in response to an external pH variation. Copyright © 2004 Society of Chemical Industry     

Syntheses and biological activities of polymers containing methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid or 5‐fluorouracil

A series of novel copolymers, poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalic acid) [poly(MTCA‐co‐ETAc)], poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐hydrogenethyl‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalate) [poly(MTCA‐co‐HEET)], and poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐α‐ethoxy‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthaloyl‐5‐fluorouracil) [poly(MTCA‐co‐EETFU)], were prepared from corresponding monomers by photopolymerizations at 25°C for 48 h. The polymers were identified by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopies. The number‐average molecular weights of the fractionated polymers determined by GPC were in the range from 9400 to 14,900 and polydispersity indices were 1.2–1.4. The in vitro IC₅₀ values of polymers against mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines and mouse liver cells (AC2F) as a normal cell line were much higher compared to that of 5‐fluorouracil (5‐FU). The in vivo antitumor activities of monomers and polymers against mice bearing sarcoma 180 tumor cell line were better than those of 5‐FU. The inhibition of DNA replication and antiangiogenesis activities of MTCA and copolymers were better compared to those of 5‐FU. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 57–64, 2004     

Fabrication and improved performance of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) for packaging by addition of high molecular weight natural rubber

The packaging industry is searching for alternative materials to attain environmental sustainability. Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate (PHBV) is a semicrystalline polymer that meets this sustainability goal since it is bioderived and biodegradable. However, its brittle nature and relatively high water permeation and transmission rates make it unsuitable for packaging applications. In addition, PHBV has poor mechanical, thermal, and rheological properties above 160 °C, limiting its use in cast sheets and thermo‐formed packaging applications. To improve these properties, new blends of PHBV with high molecular weight natural rubber at 5, 10, 15, and 25% by weight were fabricated, and physico‐chemical properties of the blends were characterized. The rubber in the blends aided in the following: increased thermal stability since the complex viscosities of the blends were improved by one log over pure PHBV at 170 °C, created more uniform melting peaks attesting to improved homogeneity, decreased water permeation to a level similar to that of traditional thermoplastics; increased the elongation at break, and stabilized the Young's modulus. Therefore, these blends can potentially be used in‐place of traditional, petroleum‐based thermoplastics in cast sheets and thermoforms. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43937.     

Reinforcement and antioxidation effects of fullerenol‐containing natural rubber

Natural rubber (NR) containing fullerenol, C60‐OH, was prepared by two methods; one by mixing C60‐OH aqueous solution to NR latex followed by coagulation (wet method) and the other by mixing C60‐OH powder with solid rubber by an open roll mixer (dry method). C60‐OH mixed by wet method was homogeneously dispersed in the rubber, while one mixed by dry method was particles in the size up to 70 μm. The former exhibited large reinforcing and antiaging effect than the latter. The large antiaging effect was explained by the finding that C60‐OH had large radical scavenging ability and gel forming ability during heat treatment. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010