Core-shell Impact Modifiers Research Articles

Highly-Toughened Polylactide- (PLA-) Based Ternary Blends with Significantly Enhanced Glass Transition and Melt Strength: Tailoring the Interfacial Interactions, Phase Morphology, and Performance

The inherent shortcomings of polylactide (PLA) including brittleness, low glass transition temperature, and melt strength during processing were addressed through a facile melt blending of PLA with polybutadiene-g-poly(styrene-co-acrylonitrile) (PB-g-SAN) core–shell impact modifier and poly(methyl methacrylate) (PMMA). Highly tough PLA-based ternary blends with drastically enhanced glass transition temperature (≈ 21 °C) and melt strength were successfully prepared. The effect of PMMA content (ranging from 0 to 30 wt %) on the phase miscibility, morphology, mechanical properties, thermal behavior, rheological properties, and toughening mechanisms of PLA/PB-g-SAN/PMMA blends with 30% PB-g-SAN was systematically investigated. It was found that PMMA can effectively tune the interfacial interactions, phase morphology and performance of incompatible PLA/PB-g-SAN blend owing to its partial miscibility with PLA matrix and miscibility with SAN shell of PB-g-SAN, as evidenced by DMTA analysis. Increase in PMMA cont...

Contribution of Ungrafted Segments in Core-Shell Impact Modifier in the Toughening of PBT Resins by Epoxy Functionalized Poly(Butadiene-graft-Styrene)

ABSTRACTA series of poly(butadiene-graft-styrene) core-shell impact modifiers and glycidyl methacrylate functionalized PB-g-PS (PB-g-PSG) with different glycidyl methacrylate content were synthesized by seeds emulsion polymerization. The modifiers were used to toughen poly(butylene terephthalate) resins. The results showed that poly(butylene terephthalate) was efficiently toughened by functionalized PB-g-PSG but not by poly(butadiene-graft-styrene). The introduction of glycidyl methacrylate improved the miscibility and properties. The effects of the ungrafted segments in modifiers on the properties of blends were investigated. The miscibility and properties dropped after the ungrafted segments in modifiers were separated. Results indicated that ungrafted PS segments showed positive effect on toughening of poly(butylene terephthalate).

Morphology and Mechanical Analysis of Polylactic Acid (PLA)/Core Shell Impact Modifier Blends

Polymer blend system of polylactic acid (PLA) and core shell as the impact modifier was studied. PLA was melt-blended with different amount of core shell impact modifier (0 to 30 wt.%). The PLA/core shell impact modifier was prepared by single screw extruder and injection molding machine into the required specimens. Morphological properties of the blends were investigated. Scanning electron microscopy (SEM) micrographs revealed that the addition of core shell impact modifier showed a coarser dispersed phase of voids. Dynamic mechanical analysis (DMA) tests confirmed that PLA/core shell impact modifier blends were partially miscible.

Toughening and Compatibilization of Acrylonitrile–Butadiene–Styrene/Poly (Ethylene Terephthalate) Blends Using an Oxazoline-Functionalized Impact Modifier

An oxazoline-functionalized core–shell impact modifier was synthesized between aminoethanol and acrylonitrile/butadiene/styrene high rubber powder. According to the Fourier transform infrared spectroscopy test, the nitrile groups were partially converted into oxazoline groups successfully. The oxazoline-functionalized acrylonitrile/butadiene/styrene high rubber powder was used as an impact modifier for acrylonitrile–butadiene–styrene/poly(ethylene terephthalate) blends. The differential scanning calorimeter and rheological tests demonstrated that poly(ethylene terephthalate) was partially miscible with acrylonitrile–butadiene–styrene, because the oxazoline groups of oxazoline-functionalized acrylonitrile/butadiene/styrene high rubber powder reacted with the end groups of poly(ethylene terephthalate). The results of scanning electron microscopy indicated that the morphology of acrylonitrile–butadiene–styrene/poly(ethylene terephthalate) blends with proper oxazoline-functionalized acrylonitrile/butadiene/styrene high rubber powder content was improved significantly. The best mechanical properties were achieved, When 6 wt% oxazoline-functionalized acrylonitrile/butadiene/styrene high rubber powder was added into acrylonitrile–butadiene–styrene/poly(ethylene terephthalate) blends.

The influence of the arrangement of styrene in methyl methacrylate/butadiene/styrene on the properties of PMMA/SAN/MBS blends

A series of methyl methacrylate-butadiene-styrene (MBS) core–shell impact modifiers were prepared by grafting styrene (St) and methyl methacrylate (MMA) onto polybutadiene (PB) or styrene-butadiene rubber (SBR) seed latex in emulsion polymerization. All the MBS modifiers were designed to have the same total chemical composition, and Bd/St/MMA equaled 39/31/30, which was a prerequisite for producing transparent blends with poly(MMA)/styrene-acrylonitrile (PMMA/SAN) matrix copolymers. Under this composition, different ways of arrangement for styrene in MBS led to the different structure of MBS modifier. The concentration of PB or SBR rubber of MBS in PMMA/SAN/MBS blends was kept at a constant value of 15 wt.%. The effects of arrangement of St in MBS on the mechanical and optical properties of PMMA/SAN/MBS blends were investigated. The results indicated that Izod impact strength of PMMMA/SAN/MBS blend with the amount of St grafted on core in MBS was higher than that of blend with the amount of St copolymerized with Bd in core of MBS, while the transparency of blend is opposite. From transmission electron microscopy, it was found that the arrangement of St in MBS influenced the dispersion of blend, which led to different toughness. Copyright © 2013 John Wiley & Sons, Ltd.

Preparation of core–shell impact modifier particles for PVC with nanometric shell thickness through seeded emulsion polymerization

The improvement in toughness of rigid polymers like poly(vinyl chloride) (PVC) has been of great interest for developing their applications. This could be provided by designing impact modifiers which could be blended with the polymeric matrix. Here, core–shell type impact modifier particles with different glass transition temperatures of the shell and specifically, with nanometric shell thickness were prepared through seeded emulsion polymerization. The core consisted of polybutadiene particles and the shell was made of poly(methylmethacrylate-co-butyl acrylate) that was grafted onto the surface of the seed particles. The polymerization reaction was optimized and the resulting latex particles were well characterized by several techniques such as DSC, DLS, SEM, and TEM. It was found that the core–shell particles have diameters of about 350–360 nm, including the shell with thickness of almost 20–30 nm and glass transition temperatures ranging between 70 and 120 °C. The prepared particles were blended with PVC and the corresponding impact strengths of the moldings were measured by means of Izod impact test. The impact results revealed that by decreasing T g of the shell in impact modifier particles, the impact resistance of the molded sheets increased remarkably. Also the brittle–ductile transition temperatures (BDTT) of the prepared blends were studied and an increase in BDTT was found with lowering T g of the shell.

Influence of elastomeric core–shell impact modifiers on mechanical properties of cellulose diacetate resin

Cellulose diacetate (CDA) plasticized with triacetine was blended by melting extrusion with two different kind of elastomeric core–shell impact modifiers: methyl methacrylate (MMA, shell) grafted onto styrene–butadiene–rubber (SBR, core) (MSBR) and MMA (shell) grafted onto butyl acrylate rubber (BAR, core) (MBAR). The different CDA/MSBR and CDA/MBAR blends were characterized by mechanical properties and morphological observation with various impact modifier contents. The highest impact strength was observed in the case of the blend with 5 wt% of MSBR and 3 wt% of MBAR, respectively. The tensile strength and Young’s modulus of CDA blends were decreased with increasing both MSBR and MBAR. According to SEM observation, MBAR was dispersed more effectively in CDA matrix than that of MSBR, thus indicating improved impact strength.

Influence of core–shell particles structure on the morphology and brittle‐ductile transition of PBT/ABS‐g‐GMA blends

AbstractThe performance of glycidyl methacrylate (GMA) functionalized acrylonitrile‐butadiene‐styrene core–shell impact modifiers (R‐ABS) with varied GMA content, crosslinking degree of rubber phase, core–shell ratio, and initiator type in toughening of poly(butylene terephthalate) (PBT) was investigated. Results show that 1 wt% GMA is sufficient to induce a pronounced improvement of the impact strength of PBT and too much GMA induces the crosslinking of R‐ABS. Divinylbenzene improves the crosslinking degree of polybutadiene and decreases its cavitation ability. The brittle‐ductile transition shifts to higher R‐ABS content. When the core–shell ratio of R‐ABS is beyond 70/30, compatibilization reaction is not sufficient to retard the agglomeration of core–shell particles. R‐ABS particles with the core–shell ratio between 50/50 and 60/40 are suitable. Initiator type can influence the internal structure of R‐ABS. For R‐ABS prepared with azobisisobutyronitrile (AIBN) as initiator, big subinclusion structure decreases its toughening ability. R‐ABS prepared with redox initiator shows better toughening behavior. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers

Microstructure and mechanical properties of poly (vinyl chloride) modified by silica fume / acrylic core-shell impact modifier blends

This research explored replacing acrylic core-shell impact modifier (AIM) by silica fume to toughen PVC. 100%, 75%, 50% and 25% of AIM (8 phr) were substituted by silica fume in PVC respectively, and then processed by dry blending and twin-screw extrusion. Severe silica fume agglomeration was observed by scanning electron microscope (SEM) in the PVC matrix when 8 phr pure silica fume was used and processed by screw speed of 20 rpm. Its tensile strength was thereby reduced by 38% comparing to unmodified PVC. The silica fume was successfully dispersed while the screw speed was slowed down to 10 rpm to give a stronger screw torque and a longer melt residential time in the extruder. The tensile strength was ‘recovered’ to a level comparable to unmodified PVC. Impact test were performed on all formulations extruded at 10 rpm screw speed and synergetic toughening effect was found with 50% substitution and it had the impact strength that was comparable to 8 phr pure AIM toughened PVC.

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

AbstractDifferent 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

Effect of Epoxy-Functionalised Core-Shell Particles on Properties of Poly(Butylenes Terephthalate) (PBT)

Glycidyl methacrylate (GMA) functional core-shell impact modifiers of butyl acrylate as a core and methyl methacrylate as a shell (gACR) have been prepared by a multi-step seeded emulsion polymerisation. FTIR spectroscopy results show that GMA had been grafted onto ACR and the GMA content in gACR was measured by titration of the epoxy groups. DMA was used to characterise the mechanical properties of the PBT/gACR blends. DSC results showed that the melting point of PBT shifted to lower temperature with an increase in GMA content. Scanning electron microscopy (SEM) images showed that the dispersion of gACR in PBT was uniform. The optimum recipes for gACR toughened PBT had a GMA content of 3% (wt) in gACR resins. The gACR particle size was about 350 nm and the gACR content was 20% (wt) in PBT resins. The notched impact strength of PBT/gACR blends exceeded 440 J/m. It was confirmed that functional core-shell impact modifiers are efficient in toughening PBT.

Toughening of polyvinylchloride by core–shell rubber particles: Influence of the internal structure of core–shell particles

The work focused on the influence of the internal structure of MBS core–shell impact modifiers on the properties of PVC/MBS blends. MBS was synthesized by grafting styrene and methyl methacrylate onto PB seed latex by emulsion polymerization. Different monomer feeding manners and initiators were employed to control the internal structure of core–shell particles. The investigation of the morphology of MBS showed that when styrene monomer was fed in a semicontinuous feeding manner and redox initiator was used, core–shell particles with rarely sub-inclusions could be obtained. When preswollen manner of styrene monomer and redox initiator were employed, there were a large number of small sub-inclusions in the core of MBS. When AIBN was used as initiator, large sub-inclusions could be found in the core of MBS. The results of the Izod impact tests showed that PVC/MBS blend with MBS prepared by preswollen manner had the lowest brittle–ductile transition temperature. And TEM showed that the different internal structures of core–shell particles could lead to different deformation mechanisms. While the results of transparency tests showed that the presence of the sub-inclusions in the MBS impaired the transparency of the blends.

Denture base resin was toughened by core-shell impact modifier and its impact properties.

Denture base resin was toughened by core-shell impact modifier and its impact properties.

Effect of matrix composition on the fracture behavior of rubber-modified PMMA/PVC blends

PB-g-MMA core-shell impact modifiers were synthesized by seed emulsion polymerization and impact-modified PMMA/PVC blends were prepared by melt blending PMMA, PVC and PB-g-MMA at 160 °C. The PB-g-MMA particles were dispersed uniformly in the PMMA/PVC matrix. PMMA/PVC blends were prepared in the blend ratio from 100/0 to 0/100 and the rubber content was kept 16% in all the compositions. The effects of matrix composition on the mechanical properties and morphology of the blends were studied. It was found that when the matrix was a PMMA-rich system, the sample broke in a brittle mode and crazing of the matrix was the main mechanisms of deformation. When the matrix was a PVC-rich system, the sample broke in a ductile mode and the main deformation mechanisms were cavitation of the particle and shear yielding of the matrix. There existed a transition from crazing to shear yielding in the rubber-modified PMMA/PVC blend as the matrix composition varied.

The influence of arrangement of St in MBS on the properties of PVC/MBS blends

Three series of MBS core–shell impact modifiers were prepared by grafting styrene and methyl methacrylate onto PB or SBR seed latex in emulsion polymerization. All the MBS modifiers were designed to have the same total chemical composition, and MMA/Bd/St equals 30/42/28, which is a prerequisite for producing transparent blends with PVC. Under this composition, there were three different ways of arrangement for styrene in MBS, which led to the different structure of MBS modifier. The concentration of MBS in PVC/MBS blends was kept at a constant value of 20 wt.%. The effects of arrangement of St in MBS on the mechanical and optical properties of PVC/MBS blends were studied. The notched Izod impact test results showed that the MBS with a PB homopolymer core grafted with St had a lowest brittle–ductile transition (BDT) temperature and BDT temperature increased with the amount of St copolymerized with Bd in the core of MBS. The transparency of blends also increased with the amount of St copolymerized with Bd in the core. TEM results showed that the arrangement of St in MBS influenced the deformation behavior. Two deformation modes were observed in the blends: cavitation and shear yielding. When all St was grafted onto the PB rubber, both cavitation and debonding were observed, which relieve the triaxial tension and promote the shear yielding of the PVC matrix. When all St was copolymerized with Bd in MBS, no cavitation could be observed and only the shear yielding of the PVC matrix took place.

About morphology in ethylene–propylene(-diene) copolymers-based latexes

Coatings and engineering plastics often require high impact strength. This property can be achieved with tougheners. For the present paper, core-shell impact modifiers were synthesized using ethylene–propylene copolymers (EPM), ethylene–propylene-diene copolymers (EPDM) or a mixture of both types (EP(D)M) as core material, as well as poly(methyl methacrylate) (PMMA) as shell material. EP(D)M-based polymers were dispersed in water using an Ultra-Turrax ® and a high pressure homogenizer. The prepared artificial latexes were used, either without further treatment or after crosslinking, as seed latexes in the emulsion polymerization of methyl methacrylate (MMA). The free radical seeded emulsion polymerization of MMA was investigated in the presence of an oil-soluble initiator, i.e. cumene hydroperoxide (CHP), combined with a redox system, i.e. sodium formaldehyde sulfoxylate hydrate (SFS), disodium salt of ethylenediamine tetra-acetic acid (EDTA), iron (II) sulfate heptahydrate (FeSO 4). This initiation system promotes polymerization of MMA near the surface of the seed particles, partially suppressing homogeneous secondary nucleation and polymerization in the aqueous phase. Kinetic and thermodynamic considerations were used to predict the particle morphology. The monomer type, the monomer-to-rubber ratio, the monomer feed type, and crosslinking of the seed latex particles were investigated, to optimize the polymerization kinetics and the properties of the resulting dispersions. The particle morphology was determined by cryo-transmission electron microscopy (cryo-TEM). Monomer-flooded conditions led to the formation of inverted core-shell particles, whereas starved–feed MMA or MMA/styrene mixtures gave rise to partially engulfed structures, i.e. snowman-like. Crosslinking of the EP(D)M seed particles was found to be required to provide the desired core-shell structures. Finally, the obtained core-shell structured particles were used to toughen a PMMA matrix. The tensile properties of the modified PMMA matrix were investigated. The micro-morphology of modified PMMA was studied by scanning electron microscopy (SEM). Tensile tests as well as TEM and SEM analyses demonstrated that the main mechanism of deformation operating in the EP(D)M-toughened PMMA matrix is shear yielding, accompanied by debonding and cavitation processes.

Blends containing core–shell impact modifiers. Part 5 – Ductile–brittle transition temperatures in impact and slow bending

Dart drop, Charpy impact and single edge notched bending fracture tests were conducted over a range of temperatures on blends of polycarbonate (PC), poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (PSAN), and poly(vinyl chloride) (PVC) with two core–shell impact modifiers, which were based, respectively, on polybutadiene and poly(butyl acrylate-co-styrene). The Tg values of the two rubbers were −75 and −8°C, respectively. The transition from fully brittle to partially or fully ductile behaviour occurred at various temperatures TBD depending upon a number of factors, which included the Tg of the rubber phase, the choice of thermoplastic matrix, and the type of test. In disc specimens subjected to dart drop impact, ductility was observed at lower temperatures than in sharply-notched specimens tested in slow three-point bending. It is concluded that the Tg of the rubber phase generally marks a lower limit for ductility in rubbertoughened blends, but that other factors can shift the brittle–ductile transition to higher temperatures.

Blends containing core–shell impact modifiers. Part 4 – Fatigue crack growth behaviour

Fatigue crack growth measurements have been made on blends of polycarbonate (PC), poly(methyl methacrylate) (PMMA), poly(styrene-acrylonitrile) (PSAN) and poly(vinyl chloride) (PVC) with two impact modifiers. In one modifier, the particles have a polybutadiene core and a PMMA shell; in the other, there is a PMMA core, a poly(butyl acrylate-styrene) inner shell and a PMMA outer shell. The overall pattern of fatigue crack growth is similar in all eight blends, but there are significant quantitative differences in ΔKth, the threshold value of the cyclic range of stress intensity factor, and in the growth rate characteristics above ΔKth. These are related to various features seen on the fracture surfaces under the scanning electron microscope, and hence to the mechanisms of deformation and fracture near the crack tip, which include crazing, particle–matrix debonding, and ductile drawing.

Mechanical properties and fracture behavior of blends of acrylonitrile–butadiene–styrene copolymer and crystalline engineering plastics

AbstractThe aim of this investigation was to evaluate the possibility of mechanically recycling blends of ABS with minor amounts of semicrystalline engineering plastics, such as polyamide, poly(ethylene terephthalate), and poly(butylene terephthalate). Compatibilizers and a core–shell impact modifier were incorporated into the blends in order to improve the mechanical properties. The toughness values, measured by the J‐integral method, and the Charpy impact strength did not always exhibit consistent results, due to the significant difference in deformation rate and in fracture mechanism. The formation of co‐continuous structures in the blends were noted and discussed. The fibrillation in the fracture surface contributed to the toughness as measured by the J‐integral method. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2435–2448, 2002

Structure and properties of impact modified polyethylene terephthalate

In this paper, we investigate the orientation behavior of impact modified PET. Core-shell particles, a metallocene polyethylene (mPE) and glycidyl methacrylate modified mPE (gmPE) were blended with PET using single screw extrusion. Morphology, crystallinity, orientation development and mechanical properties of oriented blends were studied following different orientation conditions. It was observed that core-shell impact modifier added to PET does not affectits orientation behavior and that the particles do not deform. Non-reactive mixing with mPE does not affect the orientation developed in PET for the same draw ratio, but the stress levels are affected (higher) due to an earlier crystallization of PET. Reactive blending with gmPE enhances the orientation of PET and the stress levels when orienting are higher than for pure PET, due to an earlier crystallization of PET and strain hardening of mPE being oriented, which indicate a good adhesion at the interface. The elongation at break is affected positively in many cases with the addition of a modifier, particularly gmPE, which is an indication of an improved toughness.