Ethylene-glycidyl Methacrylate Copolymer Research Articles

Mechanically strong and fully transparent PMMA composite with greatly improved toughness and impact strength incorporating PEBA nanofibrils

Improving the tensile toughness and impact strength of poly(methyl methacrylate) (PMMA) involves a trade-off, the improvements often come at the expense of reduced tensile strength, stiffness, transparency, and other crucial properties. In this article, we report a facile method to enhance the tensile toughness and impact strength of PMMA simultaneously, without sacrificing its tensile strength, stiffness, transparency, glass transition temperature, and scratch resistance. We demonstrate that the inclusion of only 3 wt% of polyether block amide elastomer (PEBA) nanofibrils (diameters ranging from ∼ 20 to 164 nm) in PMMA and ∼ 0.6 wt% of a random ethylene-glycidyl methacrylate copolymer (E-GMA) selectively at the interface resulted in a remarkable increase of ∼ 169 % in its elongation at break, ∼188 % in tensile toughness, and ∼ 87 % in notched Izod impact strength. Importantly, by incorporating such a minimal content of rubbery materials, these improvements were attained without compromising any of its major properties. Herein, we also demonstrate that multiple crazing was the primary toughening mechanism in the composites at a slow deformation speed (i.e., tensile testing), while rubber cavitation and subsequent ductile shear yielding of the surrounding matrix (enabled by the presence of E-GMA at the interface) was the most dominant at a high deformation speed (i.e., notched Izod impact testing). The high-performance composites presented herein possess immense potential for use in applications requiring a unique combination of attributes such as high strength, stiffness, tensile toughness, impact strength, and optical transparency.

CO2-assisted fabrication of PLA foams with exceptional compressive property and heat resistance via introducing well-dispersed stereocomplex crystallites

Poly (lactic acid) (PLA) foams have been considered as one of the most promising and effective substitutes for traditional petroleum-based foams owing to their excellent biodegradability and biocompatibility. In order to enhance the compressive properties and heat resistance of PLA foams, ethylene-glycidyl methacrylate copolymer (EGMA) as a carrier was first blended with poly (D-lactic acid) (PDLA) to fabricate PDLA/EGMA masterbatches. Subsequently, the resultant masterbatches were added into poly (L-lactic acid) (PLLA) to obtain well-dispersed stereocomplex crystallites (SC). Finally, the obtained PLLA/EGMA/PDLA specimens were foamed using a confined batch foaming method with CO2. The formation of SC was verified by X-ray diffraction and differential scanning calorimetry as well as their well dispersion was proven by scanning electron microscope and rheological measurement. Compared with pure PLLA, the melt viscoelasticity and crystallization rate of PLLA/EGMA/PDLA specimens were significantly improved by virtue of the formed well-dispersed SC. For PLLA/EGMA/PDLA foams, an ameliorated cell morphology was achieved. At a PDLA content of 6 wt%, the density-specific compressive strength and modulus of PLLA/EGMA/PDLA foams were 187 % and 360 % higher than those of pure PLLA foams, respectively. Additionally, the heat resistance of the PLLA/EGMA/PDLA foams was evidently enhanced, and their volume shrinkage was only around 1 % at 90 °C for 6 h. This study provides a prospect strategy for the preparation of lightweight, environmentally friendly, biodegradable PLA foams with satisfactory compressive performance and heat resistance.

Effect of compatibilization agents and rice husk on the energy demand on the extrusion of recycled high-density polyethylene composites

The new trend of the circular economy encourages the preservation of the planet’s resources. In this sense, plastic recycling is one of the critical strategies in line with the circular economy. Rice husk is one of the principal agro-industrial waste in Ecuador. Its harnessing also promotes this trend. The energy demand in single screw extrusion has been studied to optimize production cost in extrusion process manufacturing. This study examined rice husk’s effect on the extrusion process’s energy demand using a recycled high-density polyethylene (rHDPE) with a tapered compression screw with dispersive and distributive mixers. Rice husk was reduced to a maximum particle size of 45μm. Two commercial compatibilizers based on Maleic anhydride-grafted polyethylene-octene elastomer (POE-g-MA) and ethylene-glycidyl methacrylate copolymer (E-g-MA) were used to enhance compatibility between the rice husk and the polymer matrix. The energy consumption was measured on the total energy of the extruder machine. The energy consumption (EC) and specific energy consumption (SEC) were measured to contrast the effect of the rice husk (3 wt%) and the addition of the compatibilizers. The SEC of RH/E-g-MA and RH/ POE-g-MA were at about 41.11% and 55.32%, respectively, lower than rHDPE. This work suggests that rHDPE/RH bio-composite processing incurs minor costs when coupling agents, processing conditions, and screws are carefully selected.

Processability and Physical Properties of Compatibilized Recycled HDPE/Rice Husk Biocomposites

The circular economy promotes plastic recycling, waste minimization, and sustainable materials. Hence, the use of agricultural waste and recycled plastics is an eco-friendly and economic outlook for developing eco-designed products. Moreover, new alternatives to reinforce recycled polyolefins and add value to agroindustrial byproducts are emerging to develop processable materials with reliable performance for industrial applications. In this study, post-consumer recycled high-density polyethylene (rHDPE) and ground rice husk (RH) of 20% w/w were blended in a torque rheometer with or without the following coupling agents: (i) maleic anhydride grafted polymer (MAEO) 5% w/w, (ii) neoalkoxy titanate (NAT) 1.5% w/w, and (iii) ethylene–glycidyl methacrylate copolymer (EGMA) 5% w/w. In terms of processability, the addition of RH decreased the specific energy consumption in the torque experiments with or without additives compared to neat rHDPE. Furthermore, the time to reach thermal stability in the extrusion process was improved with EGMA and MAEO compatibilizers. Tensile and impact test results showed that using coupling agents enhanced the properties of the RH composites. On the other hand, thermal properties analyzed through differential scanning calorimetry and thermogravimetric analysis showed no significant variation for all composites. The morphology of the tensile fracture surfaces was observed via scanning electron microscopy. The results show that these recycled composites are feasible for manufacturing products when an appropriate compatibilizer is used.

Role of formulation additives on the properties of thermoplastic polyether ester elastomer-based and carbon fabric-reinforced multilayer composites

In this study, multilayer carbon fabric-reinforced composites (CFRC) were manufactured by compression molding technique with the combination of carbon fabric and thermoplastic polyether ester elastomer (TPEE) composites. The TPEE-based polymer layers were prepared as binary, ternary, and quaternary composites using carbon black (CB) or N-(β-aminoethyl)-γ-aminopropyl-trimethoxysilane (AEAP) modified carbon black (mCB), ethylene-glycidyl methacrylate copolymer (EGMA) and/or paraffin oil. The effects of formulation additives on multilayer CFRC were investigated in terms of their mechanical, electrical resistivity, electrically stimulated shape memory properties and morphologies. Tensile modulus of neat TPEE included multilayer CFRC increased slightly with the addition of both mCB and oil to TPEE. The highest impact strength of 112.2 kJ/m2 was obtained for TPEE-mCB-EGMA-Oil containing CFRC multilayer composites, which was 30% higher than CFRC with neat TPEE. All modified and reinforced CFRC exhibited higher electrical conductivities than neat TPEE containing CFRC. Electrically triggered bending test showed that combination of TPEE, mCB, EGMA and oil together with carbon fabric in multilayer structure revealed 80% shape recovery ratio within less than 2 min.

Recycling of plastics with compatibilizer as raw materials for the production of automobile bumper

Recycled plastic wastes polyethylene terephthalate (PET), high-density polyethylene (HDPE) and polypropylene (PP) were studied in the presence of Ethylene glycidyl methacrylate (EGMA) copolymer com...

Combined effect of copolymers and of the mixing sequence on the rheological properties and morphology of poly(lactic acid) matrix blends

In this work, the combined effect of polyethylene grafted with acrylic acid (PEgAA) and Ethylene-Glycidyl Methacrylate (EGMA) or Ethylene-Methyl Acrylate – Glycidyl Methacrylate (EMA-GMA) copolymer and of the mixing sequence of these copolymers on the rheological properties and morphology of poly (lactic acid) (PLA) matrix blends was investigated. From torque rheometry analysis it was observed that PEgAA is more reactive with EGMA than with EMA-GMA. The reactivity between PEgAA and EGMA or EMA-GMA increased with the increase in temperature. The mixing sequence affected the rheological properties and morphology of PLA/EGMA/PEgAA and PLA/EMA-GMA/PEgAA blends. The blends containing EMA-GMA copolymer showed higher impact strength than the ones containing EGMA copolymer.

In-situ grafting of carboxylic acid terminated poly(methyl methacrylate) onto ethylene-glycidyl methacrylate copolymers:One-pot strategy to compatibilize immiscible poly(vinylidene fluoride)/ low density polyethylene blends

Reactive compatibilization is an effective strategy to improve compatibility of incompatible polymer blends. However, the strategy is usually limited to the polymer blends that one of the components contains reactive groups. In this work, we have succeeded in the reactive compatibilization of the immiscible poly(vinylidene fluoride)/low density polyethylene (PVDF/LDPE) blends of which both components do not contain the reactive groups. We simultaneously incorporated the carboxylic acid terminated poly(methyl methacrylate) (PMMA) oligomer (PMMA−COOH) and ethylene-glycidyl methacrylate copolymer (EGMA) into the PVDF/LDPE blend. The ring-opening reactions of the carboxylic acid groups of PMMA oligomer and epoxide groups on the EGMA main chains happen during the melt blending and the in-situ formed EGMA-g-PMMA graft copolymers enhance the compatibility of PVDF/LDPE blends significantly. The reactive compatibilized PVDF/LDPE blends have the elongation at break and fracture strength of 507% and 40.2 MPa, respectively, as compared with the 11% and 25.6 MPa of the uncompatibilization blends. Moreover, the architecture effects of the in-situ formed EGMA-g-PMMA by varying PMMA-COOH oligomer loadings, PMMA-COOH molecular weight and the processing time on the compatibilization efficiency have been investigated. It was found that compatibilizing efficiency increases with increasing the grafted density, the length of the side chain and the degree of reaction. This one-pot strategy with the in-situ formed graft compatibilizers in incompatible blends paves new possibility for unreactive blends by reactive compatibilization.

Effect of copolymers containing glycidyl methacrylate functional groups on the rheological, mechanical, and morphological properties of poly(ethylene terephthalate)

The aim of this work was to investigate the effect of ethylene‐glycidyl methacrylate (EGMA) and ethylene‐methyl acrylate‐glycidyl methacrylate (EMAGMA) copolymers on the rheological, mechanical, and morphological properties of Poly(ethylene terephthalate) (PET). The results of torque rheometry showed an increase in the torque of PET with the addition of EGMA and EMAGMA copolymers due to the reactions between the GMA groups present in the copolymers and the carboxyl and hydroxyl groups present in PET. The torque of PET/copolymer blends increased with the increase in the copolymer content and was more pronounced for the blends containing EGMA copolymer. X‐ray diffraction and differential scanning calorimetry analyzes showed that neat PET and the PET in PET/copolymer blends are amorphous. The addition of EGMA and EMAGMA copolymers delayed the crystallization of PET. Rheological measurements showed an increase in the viscosity at low frequencies with the addition of EGMA and EMAGMA copolymers to PET. This increase was more pronounced for PET/copolymer blends containing higher amount of copolymers and for the blends containing EGMA, corroborating the results obtained by torque rheometry. The impact strength of PET/EMAGMA blends was higher than that of PET/EGMA blends. Morphology analysis by SEM showed that PET/EMAGMA blends presented higher average dispersed phase domains size than PET/EGMA blends. POLYM. ENG. SCI., 59:683–693, 2019. © 2018 Society of Plastics Engineers

Orange is the new white: rapid curing of an ethylene-glycidyl methacrylate copolymer with a Ti-bisphenolate type catalyst

The here established crosslinking chemistry opens up a by-product free method for rapid curing of epoxy-functionalised polyethylenes.

The effect of a small amount of modified microfibrillated cellulose and ethylene–glycidyl methacrylate copolymer on the crystallization behaviors and mechanical properties of polylactic acid

With the purpose of improving the crystallization rate and toughness of polylactic acid (PLA) comprehensively, chemical modified microfibrillated cellulose (MMFC) and ethylene–glycidyl methacrylate copolymer (EGMA) were used in the preparation of the PLA/MMFC/EGMA composite. After controlled acetylation using acetic anhydride, MMFC exhibited an improved hydrophobicity, resulting in a much better dispersion in PLA matrix. To clarify the impact of MMFC on the crystallization behaviors and mechanical properties of PLA, PLA/MMFC composites with 1–20 wt% of MMFC were characterized using differential scanning calorimetry (DSC) analysis and stress–strain curves. It was revealed that in the presence of only a small amount of MMFC (3 wt%), the crystallization rate of PLA was enlarged for seven times when the crystallization occurred at 120 °C, and the tensile modulus and tensile strength were both increased by 25% compared with pure PLA. The effect of EGMA component on the crystallization and mechanical properties of PLA was considered based on the characterization of the PLA/MMFC/EGMA composite. It was confirmed from DSC thermograms that a small amount of EGMA (5 wt%) did not exhibit any negative impact on the crystallization of PLA in the case of PLA/MMFC-3 wt%/EGMA-5 wt% composite. Meanwhile, in the presence of the EGMA, PLA/MMFC-3 wt%/EGMA-5 wt% composite showed an obvious increase of elongation-at-break from 9.1 to 20.8 compared with pure PLA. A remarkable improvement of crystallization behavior and toughness of PLA was achieved due to cooperative effect of the small amount of MMFC and EGMA in the PLA composite.

Crosslinking of an ethylene-glycidyl methacrylate copolymer with amine click chemistry

Commonly used crosslinking methods for polyethylenes result in the release of harmful by-products. Here, we demonstrate that an epoxy-bearing polyethylene copolymer, which contains 8 wt% glycidyl methacrylate, can be efficiently crosslinked without by-product formation. Click chemistry based on multifunctional amine curing agents, which carry at least two functional groups separated by a flexible spacer, was used to prepare thermosets. Compounding of the crosslinker and copolymer through extrusion at 120 °C could be carried out without onset of the curing reactions. Careful adjustment of the curing time and temperature, ranging from 20 to 120 min and 160–200 °C, resulted in a high network density of at least 2.8 crosslinks per 1000 carbons at a curing agent stoichiometry of as little as 0.5 wt%.

Preparation and Characterization of High-Density Polyethylene Blends and Recycled Poly(ethylene terephthalate)

Polymer blends based on recycled high density polyethylene (rHDPE) and recycled poly (ethylene terephthalate) (rPET) with two types of ethylene-glycidyl methacrylate copolymer (E-GMA), Lotader AX8840 and Lotader AX8900 as compatibilizer were produced in a co-rotating twin screw extruder. The effects of adding rPET content on the impact properties of rHDPE-rich blends were also investigated. The result showed an enhancement of about 80-270% in impact properties as compared to those of the Lotader AX8900. The impact strength also showed a decreasing trend as the rPET content was increased. The addition of E-GMA to the rHDPE/rPET blends was found to recover the blend toughness as well as improving the compatibility between HDPE and PET. In this study, the highest result was obtained for the rHDPE/rPET blends using Lotader AX8840 composition with 7.5% E-GMA content. FTIR analysis of the compatibilized blends confirmed the chemical interaction and improved interfacial bonding between the two phases.

Rice husk flour biocomposites based on recycled high-density polyethylene/polyethylene terephthalate blend: effect of high filler loading on physical, mechanical and thermal properties

Biocomposites of recycled high-density polyethylene (rHDPE)/recycled polyethylene terephthalate (rPET) matrices with a high loading of rice husk flour (RHF) were fabricated through a two-step extrusion. The use of ethylene-glycidyl methacrylate (E-GMA) copolymer improved the compatibility of the immiscible rHDPE/rPET blend. Maleic anhydride polyethylene (MAPE) was used as a coupling agent to increase the adhesion of the fibre–matrix interface. In this study, the effect of natural fibre loadings on rHDPE/rPET blends was examined. The water absorption process in the RHF-filled composites followed the kinetics and mechanisms of Fickian diffusion. Compared with samples without RHF, the rHDPE/rPET/RHF system had 58–172% higher tensile modulus and 80–305% flexural modulus. The thermal stability of the composites slightly increased with the addition of the RHF filler. The storage modulus of biocomposites was greatly enhanced by RHF. From these results, we can conclude that RHF can work well with rHDPE/rPET for manufacturing high loading biocomposite products.

Influence of Blend Composition and Compatibilizer on Mechanical and Morphological Properties of Recycled HDPE/PET Blends

Polymer blends based on recycled high density polyethylene (rHDPE) and recycled poly(ethylene terephthalate) (rPET) with and without ethylene-glycidyl methacrylate copolymer (E-GMA) as compatibilizer were fabricated in a co-rotating twin screw extruder. The effects of rPET and compatibilizer content on the mechanical properties and morphological stability of rHDPE-rich blends were investigated. The rHDPE/rPET (75/25 wt/wt) blend compatibilized with 5 php (per 100 part of polymer) E-GMA showed an enhancement of about 7% - 26% in tensile properties and flexural strength as compared with those of the neat rHDPE. The strain at break showed a decreasing trend as the rPET content increased. The addition of E-GMA to the rHDPE/rPET blends was found to recover the blend toughness as well as improving the compatibility between HDPE and PET. In this study, the highest strain at break was obtained for the rHDPE/rPET blends at 75/25 (wt/wt) composition with E-GMA content of 5 php. FTIR and SEM analysis of the compatibilized blends confirmed the chemical interaction and improved interfacial bonding between the two phases.

The compatible and mechanical properties of biodegradable poly(Lactic Acid)/ethylene glycidyl methacrylate copolymer blends

The Fourier transform infrared results suggest that the carboxylic acid groups of poly(lactic acid) (PLA) molecules react with the epoxy groups of molecules of Ethylene Glycidyl Methacrylate Copolymer (EGMC) during the reactive extrusion processes of PLAxEGMCy specimens. The tensile and tear strength values of PLAxEGMCy blown-film specimens in machine and transverse directions improve significantly, and reach their maximal values as their EGMC contents approach an optimum value of 6 wt.%. The melt shear viscosity values of PLAxEGMCy resins, measured at varying shear rates, are significantly higher than those of the PLA resin, and increase consistently with their EGMC contents. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) of PLA and PLAxEGMCy specimens reveal that the percentage crystallinity, peak melting temperature, and onset re-crystallization temperature values of PLAxEGMCy specimens reduce gradually as their EGMC contents increase. In contrast, the glass transition temperatures of PLAxEGMCy specimens increase gradually in conjunction with their EGMC contents. Demarcated porous morphology with several connected fungi-decomposed cavities was found on the surfaces of the PLAxEGMCy specimens after being buried for specific amounts of time, in which the sizes of the fungi-decomposed cavities found on the surfaces of buried PLAxEGMCy specimens reduce significantly as their EGMC contents increase. Further DMA and morphological analysis of PLAxEGMCy specimens reveal that the EGMC molecules are compatible with PLA molecules at EGMC contents equal to or less than 2 wt.% because no phase-separated EGMC droplets and tan δ transitions were found on fracture surfaces and tan δ curves of PLAxEGMCy specimens, respectively. The possible reasons for these remarkable properties of the PLA/EGMC specimens are proposed in this study.

Reactive compatibilization of poly(lactic acid)/polyethylene octene copolymer blends with ethylene-glycidyl methacrylate copolymer

AbstractA melt blending process was used to prepare poly(lactic acid) (PLA)/metallocene catalyzed polyethylene octene copolymer (POE) blends in order to toughen PLA. A commercialized ethylene-glycidyl methacrylate copolymer (EGMA) was applied as a compatibilizer to improve the dispersion and interaction of dispersed POE to the PLA matrix. The results showed that chemical interaction seems to be the driving force for reinforcing the compatibility between PLA and POE, and also the dispersion of POE into the PLA matrix domain. With the incorporation of 10 phr EGMA in the blends, POE was well-dispersed at a sub-micrometer scale within the PLA matrix, indicating better interfacial compatibility between PLA and POE. The impact strength test revealed that POE could significantly toughen PLA containing EGMA in the blends, up to no-break level regarding unnotched Izod impact strength at 10 phr EGMA content. With the increase of EGMA content, the blends showed lower tensile strength, but higher elongation at break due to the elastomeric characteristics of EGMA. When 10 phr of the EGMA was incorporated into the blends, its elongation at break reached 54.5%, 10.7 times that of neat PLA at 5.1%. The melt viscosity of compatibilized blends containing 10 phr EGMA increased by more than 50% in comparison with the non-compatibilized blend, which implied a good interfacial interaction between the PLA and POE interface.

Morphology, Rheology, and Mechanical Properties of Polylactide/Poly(Ethylene-co-octene) Blends

Polylactide (PLA)/poly(ethylene-co-octene) (POE) blends containing ethylene-glycidyl methacrylate copolymer (EGMA) as a compatibilizer were prepared by melt blending. An immiscible, two-phase structure with POE dispersed in the PLA matrix was observed by scanning electron microscopy. It was found that the POE particle size was significantly decreased by the addition of EGMA, and the POE particle size and distribution decreased with the increase of the compatibilizer content up to 2% EGMA, beyond which the POE particle size and distribution remained unchanged. The reactions between the epoxy groups of EGMA and carboxylic or hydroxyl groups of PLA were elucidated by the Fourier transform infrared spectroscopy. Rheological results showed that the G′(ω), G″(ω), and complex viscosity of PLA/POE blends significantly increased at low frequencies with the addition of EGMA. The failure mode changed from brittle fracture of the neat PLA to ductile fracture of the PLA/POE blends.

Influence of the reactive processing of recycled poly(ethylene terephthalate)/poly(ethylene‐co‐glycidyl methacrylate) blends

AbstractThe effect of the amount of reactive additive and screw speed during extrusion on the morphological characteristics and mechanical performance of recycled poly(ethylene terephthalate)(RPET) was investigated. With an increase in the ethylene–glycidyl methacrylate copolymer (E–GMA) additive content, a gradual increase in the Izod impact strength of the RPET/E–GMA blends was initially recorded. Subsequent increases in the E–GMA content to above 13.5 wt % led to a drastic enhancement in the toughness of the blends. Meanwhile, the density of the blends decreased with increasing amount of the additive E–GMA. The toughness and density of the blends were found to be dependent on the screw rotation speed during the extrusion. In addition, ductile and microporous structures were observed on the Izod impact fracture surfaces. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Preparation and Characterization of Poly(Lactic Acid)/Ethylene Glycidyl Methacrylate Copolymer Blends

Both tensile and tear strength values of PLAxEGMCy blown-film specimens in machine and transverse directions improve significantly and reach the maximum values as their EGMC contents approach an optimum value of 6 wt%. The melt shear viscosity values of PLAxEGMCy resins measured at varying shear rates are significantly higher than those of the PLA resin and increase consistently with their EGMC contents. FT-IR analysis suggest that the carboxylic acid groups of PLA molecules react with the epoxy groups of EGMC molecules during the reactive-extrusion processes of PLAxEGMCy specimens. Further DMA and morphological analysis of PLAxEGMCy specimens reveal that EGMC molecules are phase-separated with PLA molecules at EGMC contents equal to or more than 2 wt%, since distinguished phase-separated EGMC droplets and tanδ transitions were found on fracture surfaces and tanδ curves of PLAxEGMCy specimens, respectively. Possible reasons accounting for the above interesting properties of the PLA/EGMC specimens are proposed in this study.