New evidence of the surface morphology of deproteinized natural rubber particles

Summary A new evidence of the morphology of deproteinized natural rubber (DPNR) latex particles, i.e., γ-radiation vulcanized-deproteinized NR (RV-DPNR) and deproteinized-γ-radiation vulcanized NR (DP-RVNR), was obtained by transmission electron microscopy (TEM). Micrographs of the rubber particles embedding in polystyrene, prepared by using a phase transfer/ bulk polymerization process, revealed the destruction of membrane layer surrounded the DPNR particles crosslinked by γ-ray (DP-RVNR). Received: 30 July 1998/Revised version: 17 September 1998/Accepted: 14 October 1998     

Toughness enhancement of high‐impact polystyrene based on γ‐radiation vulcanized natural rubber latex by using block copolymer

Polyisoprene‐block‐polystyrene‐block‐polyisoprene (ISI) was synthesized by the iniferter route and its use, as compared to a commercial polystyrene‐block‐polyisoprene‐block‐polystyrene (SIS), in the enhancement of the toughness of high‐impact polystyrene (HIPS), prepared by the γ‐radiation vulcanized natural rubber (RVNR) latex/phase transfer/bulk polymerization technique, was investigated. Addition of 5% SIS was adequate as an interfacial agent, which effectively increased the unnotched Izod impact energy of HIPS, whereas use of 10% of ISI was required. A long polyisoprene block with two polystyrene segments of SIS was favorable for compatibilization of HIPS. Transmission electron micrographs revealed the uniform distribution of the block copolymer at the shell region of the rubber particle. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1307–1316, 2002     

Toughness and morphology of radiation‐crosslinked natural rubber modified polystyrene

γ‐Radiation vulcanized natural rubber (RVNR)/phase transfer/suspension polymerization technique was used to prepare high‐impact polystyrene (HIPS) in bead form. The high notched Izod impact resistance of HIPS based on RVNR was observed and compared with that of unmodified PS. The impact resistance of HIPS based on RVNR was further enhanced by addition of 10% of polystyrene‐block‐polyisoprene‐block‐polystyrene copolymer. A mesh structure of all crosslinked rubber particles containing polystyrene and long crazes in HIPS were observed under electron microscopy. Copyright © 2003 Society of Chemical Industry     

Deformation mechanism of polystyrene toughened with sub‐micrometer monodisperse rubber particles

Core–shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber particles with different ratios of polybutadiene to polystyrene were prepared by emulsion polymerization through grafting styrene onto polybutadiene latex. The weight ratio of polybutadiene to polystyrene ranged from 50/50 to 90/10. These core‐shell rubber particles were then blended with polystyrene to prepare PS/PB‐g‐PS blends with a constant rubber content of 20 wt%. PB‐g‐PS particles with a lower PB/PS ratio (≤70/30) form a homogeneous dispersion in the polystyrene matrix, and the Izod notched impact strength of these blends is higher than that of commercial high‐impact polystyrene (HIPS). It is generally accepted that polystyrene can only be toughened effectively by 1–3 µm rubber particles through a toughening mechanism of multiple crazings. However, the experimental results show that polystyrene can actually be toughened by monodisperse sub‐micrometer rubber particles. Scanning electron micrographs of the fracture surface and stress‐whitening zone of blends with a PB/PS ratio of 70/30 in PB‐g‐PS copolymer reveal a novel toughening mechanism of modified polystyrene, which may be shear yielding of the matrix, promoted by cavitation. Subsequently, a compression‐induced activation method was explored to compare the PS/PB‐g‐PS blends with commercial HIPS, and the result show that the toughening mechanisms of the two samples are different. Copyright © 2006 Society of Chemical Industry     

Electron microscopic observation of uniform macroporous particles. II. Effect of DVB concentration

The electron microscopic observation of uniform and macroporous poly(styrene‐co‐divinylbenzene) particles prepared by a two‐step seeded polymerization method was performed. In the synthesis of uniform macroporous particles, the uniform polystyrene latices produced by a dispersion polymerization method with two different sizes and average molecular weights were utilized as the seed particles. The seed particles were first swollen with dibutylphthalate and then with a monomer phase, including styrene and divinylbenzene. The macroporous structure of the final particles was achieved by using a porogen mixture consisting of dibutylphthalate and linear polystyrene. The linear polystyrene part of the porogen solution was directly obtained from the seed latex. The macroporous particles with different diameters and porosities were produced by changing the divinylbenzene concentration between 25 and 100% in the repolymerization step. The effect of divinylbenzene concentration on the size and the surface morphology of the final particles were investigated by scanning electron microscopy. The internal structure of the final particles was analyzed by transmission electron microscopy. The results indicated that the average size of the final particles increased with the increasing divinylbenzene concentration. The increase in the DVB concentration also led to an increase in the average pore size. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2291–2302, 1999     

Modification of natural rubber latex. III. Natural rubber–polystyrene composite latexes synthesized using azobisisobutyronitrile as initiator

Materials which may be classified as interpenetrating polymer networks have been prepared by the in situ polymerization of styrene in natural rubber latex using azobisisobutyronitrile (AIBN) as the initiator. The resulting materials have been characterized by electron microscopy, Soxhlet extraction coupled with proton nuclear magnetic resonance spectroscopy, dynamic mechanical analysis, and stress-strain analysis. The styrene polymerizes within the natural rubber latex particles to give a relatively fine phase-separated morphology with some evidence for a limited degree of segmental mixing. Moreover, it is clear that AIBN, despite what is stated in the literature, does lead to some grafting of polystyrene, and, in addition, causes significant degradation of the natural rubber molecules when the styrene content is low.     

N-苯基马来酰亚胺/苯乙烯/聚丁二烯本体聚合中的相转变(Ⅱ) 聚合条件对相转变和橡胶相结构的影响

进行了N -苯基马来酰亚胺 (PMI) /苯乙烯 (St)在聚丁二烯 (PB)存在下的半连续本体共聚合 ,研究了聚合的操作条件及配方对聚合过程中的相转变及转相后橡胶相结构的影响 .发现提高搅拌转速使相转变提前 ,升高聚合温度、增加引发剂用量、提高PMI及橡胶含量都使转相期延迟 .降低搅拌转速、提高聚合温度和橡胶含量易使橡胶相粒径增大 ,表观接枝率上升 .在一定范围内提高过氧化二苯甲酰 (BPO)浓度也将使接枝率上升 ,但PMI的引入不利于单体在橡胶上的接枝 .     

Preparation and morphological characterization of two- and three-component natural rubber-based latex particles

Different emulsion polymerization processes allowed variation in the microstructure of composite natural rubber (NR)-based latex particles. A prevulcanized and a not-crosslinked natural rubber latex were coated with a shell of crosslinked poly(methyl methacrylate) (PMMA) or polystyrene (PS). The bipolar redox initiating system tert-butyl hydroperoxide/tetraethylene pentamine promoted a core–shell arrangement. Furthermore, PS subinclusions were introduced into the NR core. The initiators used for the subinclusion synthesis were azobisisobutyronitrile at high temperature and a redox initiation system consisting of tert-butyl hydroperoxide/dimethylaniline at low temperature. The morphology of the resulting latex interpenetrating networks (IPN) was characterized by transmission electron micros-copy (TEM) and scanning electron microscopy (SEM). Different staining methods allowed us to increase the contrast between the NR phase and the secondary polymers in the composite latex particles. A semicontinuous feeding process decreased the PS subinclusions size by a factor of 6 in comparison with a batch reaction. Depending on the NR/styrene swelling ratio, the crosslinking degree, and the polymerization temperature used, distinct differences of the phase arrangement of polymers in the latex particles were revealed. © 1996 John Wiley & Sons, Inc.     

Influence of solvent contents on the rubber‐phase particle size distribution of high‐impact polystyrene

High‐impact polystyrene (HIPS) was prepared by the bulk or low‐solvent polymerization of styrene in the presence of dissolved rubber and characterized to measure the dispersed particle size of the rubber phase. Before preparation, the prepolymerization time was established by measuring the evolution of particle size distribution of the dispersed phase as a function of reaction time. The measurement technique by laser light scattering was found to be efficient enough not only to lead to the right prepolymerization time but also to predict rubber‐phase particle size distribution. Polymerization experiments were then conducted to investigate the effect of solvent contents on the particle size distribution of the rubber phase, in which ethylbenzene was introduced as a solvent at levels of 0, 3, 10, and 15%. As the solvent content increased, the size of rubber‐phase particles initially increased, reaching a maximum, and then decreased. It is speculated that a decrease in the molecular weight of the matrix, a decrease in the viscosity ratio between polybutadiene to polystyrene phases, and a change in rubber morphology all contributed to the change in the rubber particle size of HIPS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3672–3679, 2003     

Evaluation of the potential use of ultrasound during the industrial manufacturing of high impact polystyrene

During the production of high impact polystyrene the rubber particle formation process is very important to control the final physical property balance. Besides the rubber viscosity, the presence of a copolymer to reduce the interfacial tension between the rubber and polystyrene phase is central. Such a copolymer can be added or can be made during the polymerization. In this study, it was attempted to create a block rubber in situ using ultrasound. Polybutadiene dissolved in styrene has been sonicated to create macroradicals. It was anticipated that these macroradicals would initiate the polymerization of styrene thus generating a poly(butadiene‐block‐styrene) acting as emulsifier during the production of high impact polystyrene. No evidence was found for the formation of a block copolymer but the higher reactivity and the resulting rubber particles indicate that besides rubber molecular weight reduction extra functionality was introduced on the rubber. No attempts were made to define the nature of the functionality. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nanocomposites based on high impact polystyrene/silver nanoparticles: Effect of silver nanoparticles concentration on the reaction evolution,morphology, and impact strength

Nanocomposites based on high impact polystyrene (HIPS) and silver nanoparticles (AgNPs) were synthesized via in situ bulk‐suspension polymerization adding a colloidal suspension of AgNPs in styrene from the beginning of the reaction. The concentrations of AgNPs in the final nanocomposites were 0, 0.025, 0.10, and 1.0 wt%. The rate of polymerization and free radicals concentration were found to decrease with increasing AgNPs concentration. For nanocomposites with 0.025 and 0.10 wt% of AgNPs, the phenomenon of phase inversion (PI) during the mass polymerization occurred within the same range as that for the blank HIPS. Further, the impact strength of these nanocomposites did not present any changes as compared to the blank HIPS. However, there was no sign of the PI phenomenon in the case of 1.0 wt% of AgNPs, due to a decrease in the amount of free and graft polystyrene onto the rubber chain as the free radicals concentration diminishes with an increase in AgNPs. In this case the impact strength doubles the values of the blank HIPS due to the presence of a interpenetrated polymer network of crosslinked grafted rubber and polystyrene (PS) instead of the formation of a defined morphology. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Impact behavior and fracture morphology of acrylonitrile–butadiene–styrene resins toughened by linear random styrene–isoprene–butadiene rubber

A novel toughening modifier, styrene–isoprene–butadiene rubber (SIBR), was used to improve the impact resistance and toughness of acrylonitrile–butadiene–styrene (ABS) resin via bulk polymerization. For comparison, two kinds of ABS samples were prepared: ABS‐1 was toughened by a conventional modifier (a low‐cis polybutadiene rubber/styrene–butadiene block copolymer), and ABS‐2 was toughened by SIBR. The mechanical properties, microstructures of the as‐prepared materials, and fracture surface morphology of the specimens after impact were studied by instrumented notched Izod impact tests and tensile tests, transmission electron microscopy, and scanning electron microscopy, respectively. The mechanical test results show that ABS‐2 had a much higher impact strength and elongation at break than ABS‐1. The microscopic results suggested that fracture resistance of ABS‐1 only depended on voids, shear yielding, and few crazing, which resulted in less ductile fracture behavior. Compared with ABS‐1, ABS toughened by linear random SIBR (ABS‐2) displayed the synergistic toughening effect of crazing and shear yielding, which could absorb and dissipate massive energy, and presented high ductile fracture behavior. These results were also confirmed by instrumented impact tests. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel methods for synthesis of high‐impact polystyrene with bimodal distribution of rubber particle size

By using in situ prepolymerization and radiation curing, high‐impact polystyrene (HIPS) with a bimodal distribution of the size of the rubber particles (bimodal HIPS) was synthesized in the presence of ultrafine full‐vulcanized powdered styrene–butadiene rubber (UFPSBR) and polybutadiene rubber (BR). TEM photographs indicated that UFPSBR was dispersed uniformly as a single particle with a diameter of about 100 nm. On the other hand, bimodal HIPS with different rubber particle size distributions could also be obtained by blending HIPS and UFPSBR grafting styrene (UFPSBR‐g‐St) with different grafting yields. The bimodal HIPS with the smallest rubber particle size, at about 100 nm, could be prepared by blending the monomodal HIPS containing big rubber particles with polystyrene/UFPSBR. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Toughened polystyrene containing high cis-1,4-polybutadiene rubber

High cis -1,4 -polybutadiene has been used to prepare toughened polystyrene in an attempt to improve its low temperature impact properties. A range of physical and mechanical properties was obtained by keeping the amount of rubber and the polymerization conditions constant, and varying the rate of agitation in a purpose -built reactor system. Although a good balance of tensile and impact properties is obtained at room temperature, the rubber partially crystallizes when the polyblends are cooled to below ?40°C. This should decrease the efficiency of rubber particles to create and terminate crazes. However, it is significant that the developed crystallinity decreases with the rubber phase volume, and is suppressed almost completely at about 21% rubber phase volume (RPV). The factors influencing the RPV are discussed, and a study of the phase inversion with three different types of rubber shows that its duration depends on the viscosity of the styrene/rubber system.     

Synthesis and mechanical properties of high impact polystyrene with in situ bulk polymerization toughened by one‐pot Nd‐based styrene–isoprene–butadiene terpolymer rubber

High impact polystyrene (HIPS) resins were obtained with in situ bulk polymerization toughened by styrene–isoprene–butadiene terpolymer rubber (SIBR). SIBR prepolymer was prepared through selective polymerization of styrene (St), isoprene (Ip), and butadiene (Bd) in St with [Nd]/[Al]/[Cl] catalyst. Nd‐based catalyst exhibited more favorable activity toward conjugated diene other than St, resulting in St solution of random SIBR with high cis‐1,4 stereoregularity and low St content, which was directly exposed to the free radical polymerization of St to generate HIPS. Effect of toughened rubber and the initiators [difunctional (D2) and trifunctional (T3)] were examined to attain HIPS possessing mechanical properties as follow: impact strength, 0.9–24.8 kJ/m²; tensile strength, 16.0–27.5 MPa; and elongation at break, 7.4–107.0%. Increasing SIBR matrix in HIPS improved the impact strength and decreased tensile strength. The fracture surface morphologies of HIPS specimens were studied by notched impact tests and scanning electron microscopy (SEM), illustrating that the incremental SIBR matrix presented synergistic toughening effect of crazing to enhance the ductile fracture behavior. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43979.     

橡胶接枝苯乙烯本体共聚合全程聚合动力学

研究了橡胶含量、引发方式和橡胶种类对橡胶接枝苯乙烯本体共聚合动力学的影响.研究发现,橡胶链活性中心浓度较低,橡胶对引发剂自由基的笼蔽效应和对自由基的包埋是化学引发时低顺式聚丁二烯橡胶加入后聚合速率下降的主要原因;随着橡胶中苯乙烯结构单元含量的增加,橡胶的加入对接枝聚合速率的影响逐渐降低;当橡胶的黏度较高时,橡胶加入后体系的凝胶效应将导致聚合速率的增加;与热引发聚合相比,化学引发时接枝聚苯乙烯和包埋聚苯乙烯的含量较高,故其速率的下降更明显,且在相转变点出现转折点.     

Electron microscopic observation of uniform macroporous particles. I. effect of seed latex type and diluent

Uniform and macroporous polymer particles in the size range of 5–21 μm were prepared by a multistep seeded polymerization method. The uniform polystyrene particles in the size range of 1.9–7.5 μm were used as the seed particles in the preparation of macroporous beads. The seed particles with different sizes and molecular weights were produced by dispersion polymerization, by changing the type of dispersion medium and the initiator concentration. In the synthesis of macroporous particles, a two‐step swelling procedure was employed. The seed latexes were first swollen by a low molecular‐weight organic agent (i.e., dibutyl phthalate, DBP), then by a divinylbenzene–ethylvinylbenzene isomer mixture including an oil phase soluble initiator (i.e., benzoyl peroxide). The porous structure in the final beads was achieved by the polymerization of the monomer phase within the swollen seed particles including a mixture of linear polystyrene and DBP. The initiator concentration in the repolymerization step, the seed latex type (i.e., the diameter and the molecular weight of seed latex), DBP/seed latex, and the monomer/seed latex ratios were changed to achieve uniform polymer beads with different average sizes and pore structures. The average size, the size distribution, and the surface morphology of final beads were analyzed by Scanning Electron Microscopy. The internal structure of the beads were analyzed by Transmission Electron Microscopy. The results indicated that the average size of the final particles increased with increasing the seed latex diameter, DBP/seed latex, and monomer/seed latex ratios. The average pore size decreased with decreasing the molecular weight of the seed latex and increasing the DBP/seed latex and monomer/seed latex ratios. These tendencies were explained by the viscosity change of the porogen solution used in the repolymerization step. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2271–2290, 1999     

Preparation of polystyrene–clay nanocomposites via dispersion polymerization using oligomeric styrene‐montmorillonite as stabilizer

This study describes the preparation of polystyrene–clay nanocomposite (PS‐nanocomposite) colloidal particles via free‐radical polymerization in dispersion. Montmorillonite clay (MMT) was pre‐modified using different concentrations of cationic styrene oligomeric (‘PS‐cationic’), and the subsequent modified PS‐MMT was used as stabilizer in the dispersion polymerization of styrene. The main objective of this study was to use the clay platelets as fillers to improve the thermal and mechanical properties of the final PS‐nanocomposites and as steric stabilizers in dispersion polymerization after modification with PS‐cationic. The correlation between the degree of clay modification and the morphology of the colloidal PS particles was investigated. The clay platelets were found to be encapsulated inside PS latex only when the clay surface was rendered highly hydrophobic, and stable polymer latex was obtained. The morphology of PS‐nanocomposite material (after film formation) was found to range from partially exfoliated to intercalated structure depending on the percentage of PS‐MMT loading. The impact of the modified clay loading on the monomer conversion, the polymer molecular weight, the thermal stability and the thermomechanical properties of the final PS‐nanocomposites was determined. Copyright © 2012 Society of Chemical Industry     

Radiation grafting of methyl methacrylate monomer on natural rubber latex

A method of radiation grafting of methyl methacrylate (MMA) monomer on natural rubber (NR) latex has been studied. The irradiation dose in radiation emulsion polymerization of MMA monomer was lower compared to the irradiation dose for grafting of MMA monomer on NR latex, in order to obtain the same degree of conversion. This is due to the size of the rubber particles which are quite large and, hence, not sufficient to ensure an ideal emulsion polymerization. The irradiation dose for radiation grafting of MMA monomer on latex was around 300 krad to obtain a 75% degree of conversion. However, this irradiation dose was lower compared to the irradation dose for bulk polymerization of MMA monomer, in order to obtain the same degree of conversion. This is due to the gel effect in the viscous media. Radiation grafting of MMA monomer on NR latex does not influence the pH of the latex, but influences the viscosity significantly. The viscosity of the NR latex increased with an increase in irradiation dose, due to the increase of the total solid content in the latex. The MMA monomer converted to P-MMA in NR latex was largely grafted on the NR, or at least insoluble in a solvent for P-MMA, such as acetone or toluene. The hardness of the pure gum vulcanizate with an increase in the degree of grafting or P-MMA content, but the other physical properties, such as tensile strength, modulus, elongation at break, and thermal stability, were not greatly influenced by the degree of grafting.     

Effect of the composition of structured rubber particles on the toughness of poly(methylmethacrylate)

Composite natural rubber (NR) and monodisperse poly(n-butylacrylate) (PBuA) based latex particles were tested as possible impact modifiers for a poly(methylmethacrylate) (PMMA) matrix. A continuous extrusion process was used for the incorporation of wet latexes directly into a twin-screw extruder. All latexes had been coated by a PMMA shell. Furthermore, polystyrene (PS) subinclusions were introduced into the NR core. The impact resistance of the prepared PMMA blends can be most effectively improved by NR particles containing a large weight fraction of compatibilising PMMA in the shell. The degree of crosslinking of the shell polymer has to be restricted. PBuA based latex particles of 180 nm in size are ineffective to toughen the PMMA matrix. The degree of grafting of the NR phase in core–shell particles containing PS subinclusions is not crucial. Scanning electron microscopy was used to analyse the failure processes in composite rubber particle toughened PMMA blends at fast (impact conditions) and slow (tensile testing) deformation speeds.