Effects of core‐shell particle growth manners on morphologies and properties of poly(vinyl chloride)/(methyl methacrylate–butadiene–styrene) blends

A series of methyl methacrylate‐butadiene‐styrene (MBS) core‐shell particles were synthesized by seeded emulsion polymerization. All the MBS particles are designed with the same defined chemical composition, which is a prerequisite for producing transparent blends with poly(vinyl chloride) (PVC). Three different growth manners of core‐shell particles: agglomeration of small styrene‐butadiene rubbers (SBRs) followed by styrene (ST) and methyl methacrylate (MMA) monomers grafting, agglomeration of small MBS particles and traditional MBS with single SBR rubber core, and ST/MMA shells are used. The effects of growth manners of MBS on the properties and deformation mechanism of PVC/MBS blends are studied. It is found that all the MBS particles can toughen the PVC matrix effectively, but different deformation modes are observed: cavitation in large particles, debonding at the PVC/MBS interface, rubber cavitation, and clusters of voids, respectively. In addition, it is found that the stress‐whitening extent is associated with the deformation modes. J. VINYL ADDIT. TECHNOL., 22:37–42, 2016. © 2014 Society of Plastics Engineers     

Compatibility and thermal properties of poly(acrylonitrile–butadiene–styrene) copolymer blends with poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile)

The mechanical and heat‐resistant properties of acrylonitrile–butadiene–styrene (ABS) binary and ternary blends were investigated. The relationship of compatibility and properties was discussed. The results show that poly(methyl methacrylate) (PMMA) and styrene–maleic anhydride (SMA) can improve the thermal properties of conventional ABS. The Izod impact property of ABS/PMMA blends increases significantly with the addition of PMMA, whereas that of ABS/SMA blends decreases significantly with the addition of SMA. Blends mixed with high‐viscosity PMMA are characterized by higher heat‐distortion temperature (HDT), and their heat resistance is similar to that of blends mixed with SMA. For high‐viscosity PMMA, from 10 to 20%, it is clear that blends appear at the brittle–ductile transition, which is related to the compatibility of the two phases. TEM micrographs show low‐content and high‐viscosity PMMA in large, abnormally shaped forms in the matrix. Compatibility between PMMA and ABS is dependent on both the amount and the viscosity of PMMA. When the amount of high‐viscosity PMMA varied from 10 to 20 wt %, the morphology of the ABS binary blends varied from poor to satisfactory compatibility. As the viscosity of PMMA decreases, the critical amount of PMMA needed for the compatibility of the two phases also decreases. SMA, as a compatibilizer, improved the interfacial adhesiveness of ABS and PMMA, which results in PMMA having good dispersion in the matrix. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2652–2660, 2002     

Synthesis and characterization of poly(methyl methacrylate–butyl acrylate–acrylic acid)/polyaniline core–shell nanoparticles in miniemulsion media

Conductive polymer particles, polyaniline (PANI)‐coated poly(methyl methacrylate–butyl acrylate–acrylic acid) [P(MMA–BA–AA)] nanoparticles, were prepared. The P(MMA–BA–AA)/PANI core–shell complex particles were synthesized with a two‐step miniemulsion polymerization method with P(MMA–BA–AA) as the core and PANI as the shell. The first step was to prepare the P(MMA–BA–AA) latex particles as the core via miniemulsion polymerization and then to prepare the P(MMA–BA–AA)/PANI core–shell particles. The aniline monomer was added to the mixture of water and core nanoparticles. The aniline monomer could be attracted near the outer surface of the core particles. The polymerization of aniline was started under the action of ammonium persulfate (APS). The final product was the desired core–shell nanoparticles. The morphology of the P(MMA–BA–AA) and P(MMA–BA–AA)/PANI particles was characterized with transmission electron microscopy. The core–shell structure of the P(MMA–BA–AA)/PANI composites was further determined by Fourier transform spectroscopy and ultraviolet–visible measurements. The conductive flakes made from the core–shell latexes were prepared, and the electrical conductivities of the flakes were studied. The highest conductivity of the P(MMA–BA–AA)/PANI pellets was 2.05 S/cm. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A continuous tubular reactor for core–shell latex particles

High solids content poly(butyl acrylate)/poly(methyl methacrylate) core–shell latex particles were produced using miniemulsion polymerisation in a continuous linear tubular reactor. The resulting products were and shown to be comparable to a batch process. Final solids contents of 41 and 48 wt.% were shown to be possible in a simple tubular reactor. Differential scanning calorimeter analysis indicated that core–shell particles were formed under these conditions. © 2011 Canadian Society for Chemical Engineering     

Emulsion polymerization of styrene and DEAEMA with a core–shell structure

Polystyrene–poly(N,N‐diethylamino ethyl methacrylate) (PS–PDEAEMA) particles with a core–shell morphology were prepared by seeded emulsion polymerization. Poly(oxyethylene) (POE) (n = 15 and 30) nonyl phenol and sodium lauryl sulfate (SLS) were used as emulsifiers. These two emulsifiers were selected in order to study the effect of nonionic and ionic emulsifiers on the reaction because of the basic character of DEAEMA. The core–shell morphology was investigated independently in the presence of water‐soluble potassium persulfate (KPS) and of oil‐soluble azobisisobutyronitrile (AIBN). The morphologic structure of the particles was studied using scanning electron microscopy and transmission electron microscopy. The latex particles and the polymers were characterized by differential scanning analysis, thermogravimetric analysis, and gel permeation chromatography. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1977–1985, 2000     

Surface modification effects of core–shell rubber particles on the toughening of poly(butylene terephthalate)

We toughened poly(butylene terephthalate) (PBT) by loading core–shell rubber (CSR) type impact modifiers, consisting of a rubbery poly(n‐butyl acrylate) core and a rigid poly(methyl methacrylate) shell. To optimize the dispersion of CSR particles into the PBT matrix during melt compounding, the shell surface was modified with different grafting ratios of glycidyl methacrylate (GMA) reactive with PBT chain ends. In PBT blends with a 20 wt % CSR loading, the dispersed rubbery phases showed discernible shapes depending on the grafted GMA content, from predetermined spheres with 0.25 ± 0.05 μm diameters to their aggregates in the 2–3 μm diameter range. As a result, the interparticle spacing (τ) could be controlled from 0.25 to 4.0 μm in the PBT blends containing the fixed rubber loading. The Izod impact strengths of these samples increased significantly below τ = 0.4 μm. Additional thermal and morphological analyses strongly supported the hypothesis that the marked increase in toughness of the blends was related to less ordered lamellar formation of the PBT matrix under the confined geometry. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Interfacially initiated microemulsion copolymerization: One‐stage preparation of poly(n‐butyl methacrylate)–poly(N‐vinyl pyrrolidone) core–shell nanoparticles

Interfacially initiated microemulsion copolymerizations of n‐butyl methacrylate (BMA) and N‐vinyl pyrrolidone (NVP) by the redox initiation couple of benzoyl peroxide and ferrous sulfate were carried out with Tween 80 and n‐butanol as the surfactant and cosurfactant, respectively. Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy were recorded to analyze the chemical composition of the latex particles. Transmission electron microscopy was used to observe the particle morphology and dynamic light scattering to determine the particle size. The results demonstrated that interfacially initiated microemulsion polymerization prompted the copolymerization of the water‐soluble NVP monomer with the oil‐soluble BMA monomer to form core–shell nanoparticles. The influence of the surfactant concentration, BMA amount, and temperature on the particle size and polymerization rate was investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3751–3757, 2006     

Core–shell particles to toughen epoxy resins. I. Preparation and characterization of core–shell particles

A two-stage, multistep soapless emulsion polymerization was employed to prepare various sizes of reactive core–shell particles (CSPs) with butyl acrylate (BA) as the core and methyl methacrylate (MMA) copolymerizing with various concentrations of glycidyl methacrylate (GMA) as the shell. Ethylene glycol dimethacrylate (EGDMA) was used to crosslink either the core or shell. The number of epoxy groups in a particle of the prepared CSP measured by chemical titration was close to the calculated value based on the assumption that the added GMA participated in the entire polymerization unless it was higher than 29 mol %. Similar results were also found for their solid-state ^13C-NMR spectroscopy. The MMA/GMA copolymerized and EGDMA-crosslinked shell of the CSP had a maximum glass transition temperature (T_g) of 140°C, which was decreased with the content of GMA at a rate of −1°C/mol %. However, the shell without crosslinking had a maximum T_g of 127°C, which decreased at a rate of −0.83°C/mol %. The T_g of the interphasial region between the core and shell was 65°C, which was invariant with the design variables. The T_g of the BA core was −43°C, but it could be increased to −35°C by crosslinking with EGDMA. The T_g values of the core and shell were also invariant with the size of the CSP. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2069–2078, 1998     

Study of the preparation of silicone rubber particles with core–shell structure by seeded emulsion polymerization

Silicone rubber particles with core–shell structure were prepared by polymerization of vinyl monomers in the presence of linear or cross-linked poly(dimethyl siloxane–methyl vinyl siloxane) latexes. The monomers were added in either continuous or swelled-continuous modes. Core–shell particles with poly(butyl methacrylate), or poly(methyl methacrylate), as the shell were obtained by using either addition mode. The core–shell structure was not observed for polysiloxane–polystyrene particles. The influence of monomer addition mode, the compatibilities of the monomers and their homopolymers with silicone rubber, and the reactivity ratios of the vinyl monomers with the vinyl group of linear polysiloxane particles, on the formation of the core-shell structure is discussed.     

Preparation of core–shell particles by dispersion polymerization with a poly(ethylene oxide) macroazoinitiator

A macroazoinitiator (MAI) containing a poly(ethylene oxide) (PEO) block was used with a methyl methacrylate monomer to prepare polymer particles in ethanol/H₂O solutions. The effects of the monomer/MAI ratio (RMI) and H₂O content in the solutions on the molecular weight, particle diameters, and chemical structure of the resulting polymer particles were investigated. The reaction mixtures showed three kinds of states, which were milky colloid solutions, macrogels and/or precipitations, and clear solutions. The colloid solutions were obtained in the solutions with an H₂O content of about 50–90 vol % and a RMI of 20–400. In the colloid solutions, core–shell nanospheres consisting of PEO shells and poly(methyl methacrylate) (PMMA) cores were predominantly obtained. In the specific conditions close to the area of gel and/or precipitation formation, particles connected about 0.5–5 μm in length were obtained. Multiblock copolymers nanospheres tended to be obtained with lower RMIs, and PMMA‐PEO‐PMMA tri‐bloc and/or PMMA‐PEO di‐block copolymer nanospheres were obtained with higher RMIs. The solubility of the monomer and the generated polymer in solutions may have affected the polymerization development and the state of the products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of epoxy resin on the properties of maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer toughened polyamide 6 blends

Maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer (ABS‐g‐MA) was used as an impact modifier of polyamide 6 (PA6). Epoxy resin was introduced into PA6/ABS‐g‐MA blends to further improve their properties. Notched Izod impact tests showed that the impact strength of PA6/ABS‐g‐MA could be improved from 253 to 800 J/m with the addition of epoxy resin when the ABS‐g‐MA content was set at 25 wt %. Differential scanning calorimetry results showed that the addition of epoxy resin made the crystallization temperature and melting temperature shift to lower temperatures; this indicated the decrease in the PA6 crystallization ability. Dynamic mechanical analysis testing showed that the addition of epoxy resin induced the glass‐transition temperature of PA6 and the styrene‐co‐acrylonitrile copolymer phase to shift to higher temperatures due to the chemical reactions between PA6, ABS‐g‐MA, and epoxy resin. The scanning electron microscopy results indicated that the ABS‐g‐MA copolymer dispersed into the PA6 matrix uniformly and that the phase morphology of the PA6/ABS‐g‐MA blends did not change with the addition of the epoxy resin. Transmission electron microscopy showed that the epoxy resin did not change the deformation mechanisms of the PA6/ABS‐g‐MA blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The toughness and morphology of (chlorinated poly[vinyl chloride])/(methyl methacrylate‐butadiene‐styrene) blends

A series of methyl methacrylate‐butadiene‐styrene (MBS) graft copolymers were synthesized via seeded emulsion polymerization techniques by grafting styrene and methyl methacrylate on poly(butadiene‐co‐styrene) (SBR) particles. The chlorinated poly(vinyl chloride) (CPVC)/MBS blends were obtained by melting MBS graft copolymers with CPVC resin, and the effect of the core/shell ratio of MBS graft copolymer and SBR content of CPVC/MBS blends on the mechanical properties and morphology of CPVC/MBS blends was studied. The results showed that, with the increase in the core/shell ratio, the impact strength of the blend increased and then decreased. It was found that, when the core/shell ratio was 50/50, the impact strength was about 155 J/m, and the tensile strength evidently increased. The toughness of the CPVC/MBS blend was closely related to the SBR content of the blend, and with the increasing of SBR content of blend, the impact strength of the blend increased. The morphology of CPVC/MBS blends was observed via scanning electron microscopy. Scanning electron microscopy indicated that the toughness of CPVC/MBS blend was consistence with the dispersion of MBS graft copolymers in the CPVC matrix. J. VINYL ADDIT. TECHNOL., 22:501–505, 2016. © 2015 Society of Plastics Engineers     

Structure–properties relationship in toughening of poly(butylene terephthalate) with core–shell modifier

The performance of acrylonitrile–butadiene–styrene (ABS) core–shell modifier with different grafting degree, acrylonitrile (AN) content, and core–shell ratio in toughening of poly(butylene terephthalate) (PBT) matrix was investigated. Results show PBT/ABS blends fracture in ductile mode when the grafting degree is high, and with the decrease of grafting degree PBT/ABS blends fracture in a brittle way. The surface of rubber particles cannot be covered perfectly for ABS with low grafting degree and agglomeration will take place; on the other hand, the entanglement density between SAN and PBT matrix decreases because of the low grafting degree, inducing poor interfacial adhesion. The compatibility between PBT and ABS results from the strong interaction between PBT and SAN copolymer and the interaction is influenced by AN content. Results show ABS cannot disperse in PBT matrix uniformly when AN content is zero and PBT/ABS fractures in a brittle way. With the addition of AN in ABS, PBT/ABS blends fracture in ductile mode. The core–shell ratio of ABS copolymers has important effect on PBT/ABS blends. When the core–shell ratio is higher than 60/40 or lower than 50/50, agglomeration or cocontinuous structure occurs and PBT/ABS blends display lower impact strength. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 5363–5371, 2006     

Preparation and characterization of core–shell polystyrene and polymethylsilsesquioxane structure latex particles by seeded polymerization

Composite polystyrene and polymethylsilsesquioxane (PS‐PMSSQ) latices were prepared by hydrolysis and polycondensation of triethoxylmethylsilane (TEOMS) in the presence of PS seed latices, obtained by gamma ray induced polymerization. Morphology of the composite latex particles was observed by transmission electronic microscopy and their size distribution was measured by dynamic laser light scattering. It was found that if 1 wt% silicon‐containing surfactant (SCS) and 0.4 wt% dodecylbenzene sulphonic acid (DBSA) were both used, core–shell/PS‐PMSSQ latex particles could be prepared at 30 °C. The core–shell structure was further characterized by X‐ray photoelectron spectrometry. With 0.5 wt% SCS or 0.2 wt% DBSA, the capsulation was incomplete. At 0 and 90 °C, the PMSSQ phase penetrated into the seed particles. No core–shell structure was observed when DBSA was replaced by hydrochloric acid or SCS was replaced by poly(ethylene glycol) monooctylphenyl ether. Copyright © 2006 Society of Chemical Industry     

Preparation and characterization of core–shell polystyrene–polydimethylsiloxane particles by seeded polymerization

Nanometer scale particles of seed latex were successfully prepared by polymerization induced by gamma rays. By modification of the coupling agent 3‐methacryloxylpropyltrimethoxylsilane (MPS) at the surface of polystyrene (PSt) particles, polydimethylsiloxane (PDMS) was introduced outside the PSt particles and composite latex particles with a core–shell (PSt–PDMS) structure were successfully prepared. Because of the chemical bond linkage between the core and the shell, such a structure is stable. Direct evidence of the core–shell structure was observed by transmission electron microscopy (TEM). In addition the chemical bond linkage was confirmed by Fourier‐transfer infrared (FT‐IR) spectroscopy. An indirect proof of the core–shell structure was given by water absorption ratio determination of the different samples. Copyright © 2004 Society of Chemical Industry     

Surface immobilisation of fluorinated polystyrene‐acrylate latex nanoparticles with core–shell structure by crosslinking

Fluorinated polystyrene‐acrylate (PSA) latex nanoparticles with core–shell structure were synthesised by two‐stage seeded emulsion polymerisation method in the presence of reactive emulsifier DNS‐86. Diallyl phthalate (DAP) and Vinyltriethoxysilicone (VTES) were used as crosslinking agent to immobilise the fluorinated copolymer on the surface of the latex film. Fourier transform infrared spectroscopy (FTIR) spectra show that fluorine and siloxane monomers were effectively involved in the emulsion copolymerisation. Transmission electron microscope (TEM) observation shows that the prepared emulsion particles had a core–shell structure with fluorinated copolymer in the shell. X‐ray photoelectron spectroscopy (XPS) analysis reveals that fluorine atom has the tendency of migrating to the film–air interface and the incorporation of VTES helps the migration of fluorine atom towards the film–air interface. Water contact angle (WCA) test proved that DAP and VTES as crosslinking agent can immobilise the fluorinated copolymer on the surface of the latex films. © 2011 Canadian Society for Chemical Engineering     

Influence of core–shell rubber particles synthesized with different initiation systems on the impact toughness of modified polystyrene

Core–shell poly(butadiene‐graft‐styrene) (PB‐g‐PS) rubber particles were synthesized with different initiation systems by emulsion grafting polymerization. These initiation systems included the redox initiators and an oil‐soluble initiator, 1,2‐azobisisobutyronitrile (AIBN). Then the PB‐g‐PS impact modifiers were blended with polystyrene (PS) to prepare the PS/PB‐g‐PS blends. In the condition of the same tensile yield strength on both samples, the Izod test showed that the notched impact strength of PS/PB‐g‐PS(AIBN) was 237.8 J/m, almost 7 times than that of the PS/PB‐g‐PS(redox) blend, 37.2 J/m. From transmission electron microscope (TEM) photographs, using the redox initiators, some microphase PS zones existed in the core of PB rubber particles, which is called “internal‐grafting.” This grafting way was inefficient on toughening. However, using AIBN as initiator, a great scale of PS subinclusion was seen within the PB particle core, and this microstructure increased the effective volume fraction of the rubber phase with a result of improving the toughness of modified polystyrene. The dynamic mechanical analysis (DMA) on both samples showed that the glass transition temperature (T_g) of rubber phase of PS/PB‐g‐PS(AIBN) was lower than that of PS/PB‐g‐PS(redox). As a result, the PB‐g‐PS(AIBN) had better toughening efficiency on modified polystyrene than the PB‐g‐PS(redox), which accorded with the Kerner approximate equation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 738–744, 2007     

Effect of acrylic core–shell rubber particles on the particulate flow and toughening of PVC

Different types of acrylic core–shell rubber particles with a poly(butyl acrylate) (PBA) core and a grafted poly(methyl methacrylate) (PMMA) shell were synthesized. The average size of acrylic core–shell latex particles ranged from 100 to 170 nm in diameter, having the core gel content in the range of 35–80%. The melt blending behavior of the poly(vinyl chloride) (PVC) and the acrylic core–shell rubber materials having different average particle sizes and gel contents was investigated in a batch mixing process. Although the torque curves showed that the particulate flow of the PVC in the blends was dominant, some differences were observed when the size and gel content of the particles varied. This behavior can be attributed to differences in the plasticizing effect and dispersion state of various types of core–shell rubber particles, which can vary the gelatin process of the PVC in the mixing tool. On the other hand, the highest toughening efficiency was obtained using core–shell rubber particles with the smallest particle size (i.e., 100 nm). The results showed that increasing the gel content of the core–shell impact modifiers with the same particle size improved the particle dispersion state in the PVC matrix. The toughening efficiency decreased for the blends containing 100 and 170 nm rubber particles as the gel content increased. Nevertheless, unexpected behavior was observed for the blends containing 140 nm rubber particles. It was found that a high level of toughness could be achieved if the acrylic core–shell rubber particles as small as 100 nm had a lower gel content. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The interfacial effect of TiO2–Ag core–shell micro‐/nanowires on poly(arylene ether nitrile)

Novel TiO₂–Ag core–shell micro‐/nanowires (TiO₂ shell coating on Ag core) have been successfully prepared via a solvent–thermal method. Energy dispersive spectroscopy and X‐ray diffraction analyses revealed that the micro‐/nanowires were composed of Ag, Ti and O elements, and Ag was face‐centered cubic whereas TiO₂ was mainly amorphous. Interestingly, scanning electron microscopy (SEM) and transmission electron microscopy results showed that most of the TiO₂ bristles were perpendicular to and uniformly studded on the surface of the Ag cores. Subsequently, TiO₂–Ag/poly(arylene ether nitrile) (PEN) composite films were prepared via a solution‐casting method in order to investigate the effect of TiO₂–Ag on the PEN matrix. SEM images showed that there was good interfacial adhesion between fillers and PEN matrix owing to the special bristle‐like structure. Thermal analysis results showed that the TiO₂–Ag/PEN composite films possessed excellent thermal properties endowed by the PEN matrix. The dielectric constant of the composite films increased to 9.3 at 100 Hz when the TiO₂–Ag loading reached 40 wt%. Rheology measurements revealed that the network formed by TiO₂–Ag was sensitive to shear stress and nearly time independent. © 2013 Society of Chemical Industry