Ethylene Acrylic Acid Research Articles

Rapidly Responding pH- and Temperature-Responsive Poly (N-Isopropylacrylamide)-Based Microgels and Assemblies.

Rapidly responding stimuli-responsive materials can have a benefit in a myriad of applications, for example, sensing and biosensing, actuation, and in drug delivery systems. Thermo- and pH-responsive materials have been among the most widely studied, and can be triggered at physiologically relevant temperatures and pH. Here, we have used a “homologous series” of acids based on the acrylic acid (AAc) backbone and incorporated them into N-isopropylacrylamide (NIPAm)-based microgels. Specifically, the acids used were AAc, methacrylic acid (MAAc), ethylacrylic acid (EAAc), and butylacrylic acid (BAAc), which have pKa’s in the range of 4.25–7.4. The resultant microgels were characterized by optical microscopy, and their responsivity to temperature and pH studied by dynamic light scattering. The microgels were subsequently used to generate optical devices (etalons) and their pH and temperature response was also investigated. We found that the devices composed of BAAc-modified microgels exhibit unusually fast response kinetics relative to those of the rest of the devices. We also found that the speed of the response decreased as the length of the acid pendant group decreased, with AAc-modified microgel-based devices exhibiting the slowest response kinetics. Finally, we showed that the kinetics of the device’s temperature response also decreased as the length of the acid pendant group decreased, which we hypothesize is a consequence of the hydrophobicity of the acid groups, that is, increased hydrophobicity leads to faster responses. Understanding this behavior can lead to the rational design of fast responding materials for the applications mentioned above.

Dow and DuPont submit package to regulators

Dow Chemical and DuPont have submitted a remedy package to the European Commission in the hope that the proposed divestitures will be enough to appease antitrust regulators and complete their merger. The companies say they are willing to part with a portion of DuPont’s crop protection business, including associated R&D operations, as well as Dow’s acid copolymers and ionomers business. Indeed, earlier this month, Dow agreed to sell its ethylene acrylic acid copolymers business to South Korea’s SK Global Chemical. As a result of this submission, the EC is extending its review of the merger until April 4.

Dow will sell polymer unit to SK

As part of its bid to get its merger with DuPont past antitrust regulators, Dow Chemical has agreed to sell its Primacor ethylene acrylic acid (EAA) copolymers business to South Korea’s SK Global Chemical for $370 million. The deal includes plants in Freeport, Texas, and Tarragona, Spain. DuPont operates an EAA business under the Nucrel name. Such polymers act as an adhesive layer in packages containing metal foil. The two companies continue to negotiate with regulators about their combined agricultural businesses.

Influence of carbon black and carbon nanotubes on the conductivity, morphology, and rheology of conductive ternary polymer blends

The influence of carbon black (CB) and multiwall carbon nanotubes (CNT) with different colloidal properties on the phase morphology, electrical properties, and rheological behavior in a polypropylene (PP)/poly(methyl methacrylate) (PMMA)/ethylene acrylic acid copolymer (EAA) ternary polymer blend was studied. A PP/PMMA/(EAA‐CNT) system was compared to two different PP/PMMA/(EAA‐CB) systems. The relationship between the phase morphology, electrical percolation threshold, and rheological behavior was analyzed. The critical percolation threshold for the ternary system was found to be around 0.5 vol% for the PP/PMMA/(EAA‐CB1) and 0.2 vol% for the PP/PMMA/(EAA‐CB2) and PP/PMMA/(EAA‐CNT), which were more than 8 times lower than for the single phase systems. The rheological threshold coincided with the electrical resistivity percolation threshold inversion point. It was proposed that beyond a critical loading of conductive filler particles in the minor EAA phase, especially for high aspect ratio fillers such as the CB2 and CNT, phase separation is slowed significantly due to the aggregation of particles into a network formation within the EAA phase causing a significant increase in phase viscosity. The results are consistent with the hypothesis that the kinetics of phase separation and resulting formation of a tri‐continuous morphology are dictated by the viscosity of the minor phase relative to the two major phases. POLYM. ENG. SCI., 57:1329–1339, 2017. © 2017 Society of Plastics Engineers

Experimental and numerical analysis of conductive ternary polymer blend composites

ABSTRACTExperimental and theoretical analysis of the phase morphology and electrical conductivity of a carbon black (CB)‐filled polypropylene /poly(methyl methacrylate) /ethylene acrylic acid copolymer ternary system were compared. The Cahn‐Hilliard theory was used to model and predict the phase morphology and electrical conductivity as a function of the constituents' characteristics of the ternary system. A method for generating statistically representative microstructures of a co‐continuous ternary polymer system and a numerical method for calculating the resultant electrical conductivity of these ternary polymer systems are presented. Excellent agreement between numerically calculated and experimentally measured results was observed. The developed analytical and numerical models were able to successfully predict the electrical percolation threshold with that of ternary polymer composites containing CB as a conductive medium with minimal experimental input. The combination of experimental and numerical results presented suggests the optimization of the conductive minor phase includes having a conductivity beyond the critical percolation threshold, is at least three orders of magnitude greater than either of the two nonconductive phases, and has a lower viscosity than the other two major phases in order to maximize the phase separation kinetics. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44749.

Structural, Thermal and Optical Properties of Mn2+ Doped Methacrylic Acid – Ethyl Acrylate (MAA:EA) Copolymer Films

Abstract Pure and Mn2+ doped Methacrylic Acid Ethylacrylate (MAA:EA) copolymer films were prepared by using the solution cast technique. Investigations were conducted using DSC, TGA, XRD, FTIR, UV–Vis, SEM and EPR. Thermal properties of these films were investigated with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Using the DSC thermograms, glass transition temperature (Tg ) and melting temperature (Tm ) of copolymer films were measured. Thermogravimetric curves of the pure and Mn2+ doped MAA:EA copolymer showed two distinct steps of weight loss. The optical absorbance of the pure and Mn2+ doped films were measured in the 200–800 nm wavelength range. The values of absorption edge, direct and indirect band gaps were calculated. The optical band gap decreased with the increase of mol% of Mn2+ ions. The enhanced amorphous nature of the doped copolymer has been identified from X-ray diffraction analysis. FTIR spectral studies of pure and Mn2+ doped MAA:EA copolymer films display significant structural changes within the copolymer film indicating the complexation. The morphology of the copolymer samples was examined by scanning electron microscopy (SEM). EPR spectra of all the doped samples exhibit a single absorption line centered at g=2.005. The observed variation in the EPR signal intensity is due to the existence of interacting paramagnetic centers.

Modification of Polylactic Acid by Ethylene-Acrylic Acid Copolymer and Nano-Sized Octamaleamic Acid Polyhedral Oligomeric Silsesquioxane

Modification of Polylactic Acid by Ethylene-Acrylic Acid Copolymer and Nano-Sized Octamaleamic Acid Polyhedral Oligomeric Silsesquioxane

Joining Mechanism of Dissimilar Materials such as Metal and Plastic Sheets by Friction Lap Joining

It is difficult to join dissimilar materials such as metallic material and polymer. We have investigated to join Aluminum alloy and high density polyethylene (PE) and ethylene acrylic acid copolymer (EAA) using Friction Lap Joining (FLJ) and then concluded EAA could be strongly joined with Aluminum alloy. PE could not be joined without anodizing. We have considered that EAA has a polar functional group, COOH. On the contrary, PE cannot be joined to an as-received aluminum alloy, because PE has no polar functional group. So, we have tried to confirm this mechanism with XPS and FTIR to investigate the interface between anodized surface and that of polymer. We find that the possibility of chemical bonding arises between O-H in COOH and O in Al2O3or O in C=O and O in Al2O3 at elevated temperature.

Morphology and mechanical properties of polypropylene/ethylene acrylic acid/maleic anhybride-grafted polypropylene/organoclay nanocomposites

Polypropylene (PP)/ethylene acrylic acid (EAA)/maleic anhybride-grafted PP (PP- g-MA)/organoclay nanocomposites were prepared using the melt mixing technique, and PP- g-MA and EAA were employed as the compatibilizers. The sodium montmorillonite (MMT) were pretreated with high-speed airflow pulverization method and then grafted using γ-glycidoxypropyltrimethoxysilane, followed by modification using trihexyltetradecylphosphonium chloride cation with supercritical carbon dioxide as the reaction medium (the obtained product was abbreviated as OGMMT). The modification of MMT was characterized by thermogravimetric analysis, X-ray diffraction (XRD), and scanning electron microscopy. The effect of organoclay content on microstructure and mechanical properties of PP/EAA/PP- g-MA/OGMMT nanocomposites was investigated by XRD, transmission electron microscopy, dynamic mechanical analysis, tensile strength, notched impact strength, flexural strength, and flexural modulus. The results show that the OGMMT has a high weight loss, a large d-spacing increment, and exfoliation predomination structure. The addition of compatibilizers benefited the formation of exfoliated structure and the dispersion of OGMMT in PP matrix, and hence, enhanced the storage modulus ( G′) below the glass transition temperature ( Tg), storage modulus ( G″), Tg, tensile strength, flexural strength, and flexural modulus of the nanocomposites. Furthermore, with the increasing OGMMT content, the nanocomposites exhibited very inconsiderable alteration in the clay dispersion level and enhanced G′ below the Tg, G″, tensile strength, flexural strength, and flexural modulus of the nanocomposites, whereas the Tg was invariant. As a whole, the introduction of compatibilizers and OGMMT led to the reduction of notched impact strength, which also nearly linearly decreased with increasing clay content.

The impact of interfaces in laminated packaging on transport of carboxylic acids

The permeability of oleic and acetic acid through low density polyethylene (LDPE) and ethylene acrylic acid (EAA) have been measured using diffusion cells. In addition, the permeability through combinations of LDPE and EAA in the form of laminates with different numbers of layers has been determined. Oleic acid shows an almost 30 times higher permeability compared to acetic acid, which was partly explained by the adsorption of oleic acid to the film surface during the permeability experiment. In addition, the permeability is lower for both oleic and acetic acid in the laminates compared to the pure films. The decreased permeability can be explained by the presence of crystalline domains close to the interface. This is supported by SAXS data which suggests an ordering of polymer chains in the EAA film close to the interface. In summary, the results show that it is possible to create barrier materials with decreased permeability, which is interesting for example in the packaging industry.

New blends of ethylene-butyl acrylate copolymers with thermoplastic starch. Characterization and bacterial biodegradation

Ethylene-butyl acrylate copolymer (EBA) with 13% of butyl acrylate content was used to produce blends with 10, 30 and 60% of thermoplastic starch (TPS) plasticized with glycerol. Ethylene-acrylic acid copolymer (EAA) was used as compatibilizer at 20% content with respect to EBA. The blends were characterized by X-ray diffraction, ATR-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM), water-Contact Angle measurements (CA), Differential Scanning Calorimetry (DSC) and Stress–strain mechanical tests. Initiated autoxidation of the polymer blends was studied by chemiluminescence (CL) confirming that the presence of the polyolefin-TPS interphase did not substantially affect the oxidative thermostability of the materials. Three bacterial species have been isolated from the blend films buried in soil and identified as Bacillus subtilis, Bacillus borstelensis and Bacillus licheniformis. Biodegradation of the blends (28days at 45°C) was evaluated by carbon dioxide measurement using the indirect impedance technique.

Investigation of alumina samples cast from concentrated polymer suspensions

In this research we investigated a new ceramic forming process. The technology is based on a concentrated ceramic suspension with ethylene acrylic acid copolymer binder system. After the forming procedure to get the final products, the samples were dried, debinded and sintered on high temperature. The samples were studied by different ways during the process: rheological studies, surface properties (optical and scanning electron microscopy), mercury porosimetry.

3,3-Dibromo-2-trifluoromethyl acrylic acid ethyl ester: a versatile platform for the stereoselective preparation of functionalized-α-trifluoromethyl α,β-unsaturated lactones and trifluoromethyl pyrazolinones

Synthetic routes to multi-functionalized-α-trifluoromethyl α,β-unsaturated lactones and trifluoromethyl pyrazolinones.

아크릴계 점착부여제의 제조 및 이를 함유한 아크릴계 점착제의 물리적 특성

An acrylate tackifier was prepared for producing high performance acrylic pres- sure-sensitive adhesives (PSAs). PSAs exhibiting high adhesion values were prepared using 2-ethyl hexylacrylate (2-EHA), 2-carboxyethyl acrylate (β-CEA), and acrylic acid (AA) mono- mers. The acrylate tackifier was prepared using an acrylic monomer for improving its com- patibility with the acrylic PSA. The weight-average molecular weights of PSA and the acrylate tackifier were found to be around 1.2×10 6 g/mol and 20,000−40,000 g/mol, respectively. Physical properties (such as the peel strength, tack, and the holding power) of the mixtures of acrylic PSA with different acrylate tackifiers were enhanced with an increase in the amount of tackifier added.

Mathematical modeling for the prediction of the overall swelling profile from poly (AM-co-AA-co-HEA) hydrogels: effect of glycidyl methacrylate and ammonium per sulphate

In the present investigation, a series of hydrogels based on poly (AM-co-AA-co-HEA) from the constant weight ratio (1/1/1) of acrylamide (AM), acrylic acid (AA), and hydroxy ethyl acrylate (HEA) monomers were synthesized by solution polymerization to optimize the reaction conditions. The reaction conditions were optimized by varying the reaction temperature, reaction time, crosslinker and initiator concentration, and amount of solvent. At optimized reaction conditions, two different sets of hydrogels were synthesized by varying the concentrations of cross-linker (glycidyl methacrylate, GMA) from 1 to 4 % and initiator (ammonium per sulphate, APS) from 1 to 4 %, to study the effects of crosslinker variation as well as initiator variation on swelling ratio by Flory’s equations. The three mathematical models (early time, late time and etters model) were fitted on experimental swelling data to investigate the entire swelling profile of all the hydrogels prepared with various amounts of GMA and APS content. Values of swelling transport exponents showed that the swelling mechanism was shifted from diffusion to relaxation controlled in case of increasing APS content, while only diffusion mechanism was followed for increasing GMA content. The proportionality constant (k) was calculated by two different models (1) power law and (2) Baker and Lonsdale to confirm the validity of early-time model fitting on experimental swelling data.

Influence of Dioctyl Maleate Concentration on Performance Behavior of Water Based Pressure-sensitive Adhesives via Reversible Addition–Fragmentation Chain Transfer Emulsion Polymerization

Reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization was successfully applied for the synthesis of pressure-sensitive adhesives (PSAs) of predetermined molar mass and of low polydispersity index (PDI). The performances of the adhesives were investigated by testing tack, peel, and shear resistance on seven different substrates (coated paper, uncoated paper, polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BOPP), aluminum strip, low linear density polyethylene (LLDPE), and low density polyethylene (LDPE). The influence of monomer composition on the adhesive performance was evaluated by varying the molar ratio of butyl acrylate (BA)/dioctyl maleate (DOM) while keeping the molar ratio of acrylic acid (AA) and 2-hydroxy ethyl acrylate (2-HEA) constant. As the DOM content increased, shear, peel strength, and loop tack were found to increase. It was noted that the adhesive properties of PSAs can be tailored by incorporating small amounts of hydrophobic DOM into the PSAs, which significantly increases the peel and shear strength of the resulting PSAs. Carboxyl terminated bifunctional trithiocarbonate RAFT agent possess the strong potential to polymerize hydrophobic DOM in aqueous phase and exhibit better living character with PDI less than 1.5.

The role of functional monomers on producing nanostructured lattices obtained by surfactant-free emulsion polymerization – A novel approach

Nanostructured lattices were prepared in a single step emulsion polymerization reaction in the absence of surfactants by exploring the so called “pickering” stabilization mechanism. The synthesis protocol and the properties of the obtained particles were evaluated and discussed simultaneously considering processing and formulation aspects with special emphasis to the chemical properties of the functional monomers selected on the present study. Colloidal silica was used to ensure the physical stability required to produce nanoparticles as a result of the emulsion polymerization route. Three different monomers including methyl metacrylate (MMA), styrene (Sty) and vinyl acetate (VAC) were used to structure the particles of interest. Four different functional polymers including acrylic acid (AA), styrene sulfonate (StySO3), hydroxyethyl methacrylate (HEMA) and dymethylamino ethyl methacrylate (DMAEMA) were evaluated.The obtained lattices were comparatively characterized regarding to surface tension, particle size distribution, morphological aspects, viscosity, zeta potential and colloidal stability.The one-step pickering emulsion polymerization proved to be an effective approach to prepare lattices of industrial interest without the use of surfactants. The obtained particles presented average mean diameters ranging from 155 to 345nm with relatively low polydispersity indices (0.39–2.02). The most promising behavior was experimentally verified once selecting the styrene sulfonate (StySO3) as the functional monomer. The hydroxyethyl methacrylate (HEMA) also proved to be an interesting alternative although its limitation related to high surface tension applications. The high resolution images registered with the HRSEM-FEG technique explicit morphological aspects that effectively contribute to elucidate the “pickering” stabilization mechanism and the resultant core–shell structure derived thereof.

Effect of compatibilizer and organoclay content on structure, thermal, and mechanical properties of poly(butylene succinate)/(Ethylene acrylic acid)/Organoclay nanocomposites

Poly(butylene succinate) (PBS)/(ethylene acrylic acid) (EAA)/organoclay nanocomposites were prepared by using the melt intercalation technique. EAA was used as compatibilizer and organoclay was used as inorganic filler. X-ray diffraction and transmission electron microscopy results indicated the addition of compatibilizer led to a large increase in basal spacing of nanocomposites and better overall dispersion of organoclay in the PBS matrix. However, the basal spacing was found to be invariant as the organoclay content increased. The differential scanning calorimetry analyses revealed that the incorporation of the organoclay and EAA and the variation of organoclay content altered the melting behavior and crystallization properties of PBS. Storage and loss modulus of virgin matrix increased with the incorporation of organoclay and EAA, and a maximum for the nanocomposite with 9 wt% organoclay. Moreover, the glass transition temperatures also increased for the various organoclay-containing samples. Mechanical properties showed an increase with the incorporation of organoclay and EAA. The 5 wt% organoclay-filled PBS gave the highest tensile strength and notched Izod impact strength among all the composites. Further increments in organoclay loading reduced the tensile strength and notched impact strength of nanocomposites, which was thought to be the result of agglomeration. However, increments in clay loading enhanced the flexural strength and flexural modulus of nanocomposites, with a maximum at 9 wt% organoclay. J. VINYL ADDIT. TECHNOL., 2015. © 2015 Society of Plastics Engineers

Effect of amphiphilic compatibilizers on the filler dispersion and properties of polyethylene—thermally reduced graphene nanocomposites

ABSTRACTCompatibilizers of different chemical structures and specifications were used to enhance the filler exfoliation in nanocomposites of polyethylene and thermally reduced graphene prepared by melt mixing route. The mechanical performance of the compatibilized nanocomposites was observed to be better than PE/G nanocomposites due to enhanced extent of filler exfoliation and distribution. Highest increase of 45% in tensile modulus and 13% in peak stress was observed in the composites. Overall, from the mechanical, rheological, thermal, and calorimetric properties, the compatibilizers with best performance were ethylene acrylic acid (EAA) copolymer and chlorinated polyethylene (CPE25). Furthermore, the extent of filler exfoliation was observed to increase with increasing EAA content thus confirming positive interactions between EAA and thermally reduced graphene, though no specific chemical interactions could be detected. The composite properties were observed to reach maximum around 7.5 wt % EAA content, followed by reduced performance due to extensive matrix plasticization. The observed behaviors were a result of interplay of opposing factors like filler exfoliation due to compatibilizer addition and matrix plasticization due to its lower molecular weight, thus the observed optimum comaptibilizer amount was specific to the compatibilizer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42484.

Evaluation of ethylene–acrylic acid copolymer (EAA)-modified asphalt: Fundamental investigations on mechanical and rheological properties

Asphalt should be modified before construction on account of the weakness in performance such as flowability at high temperature and brittleness at low temperature. Polymer modified asphalt (PMA) is the most effective valuable method acknowledged by all researchers in this field. Ethylene–acrylic acid copolymer (EAA) is compounded by ethylene and acrylic acid, which has no unsaturated bond, thus it could enhance asphalt a better performance in aging resistance and stability. Moreover, acrylic acid chains in EAA could have a strong binding force with alkaline aggregate. In this paper, three different types of EAA with different acrylic acid content were adopted to modify the asphalt. Softening points, penetration, viscosity, storage stability at high temperature, microstructure, rheological properties and adhesive capacity of the modified asphalt were investigated. Results showed that, with adding more EAAs, softening point and viscosity of the modified asphalt were both increasing while penetration decreased. Softening point approached to 60.5°C from 46°C at EAA 1321 content of 10% by weight. For the same dosage of different types of EAA, the properties of modified asphalts were mainly affected by the melting index of EAA since the content of EAA was less than 6wt%. When EAA content was more than 6%, the properties of the asphalts were evolved with the change of acrylic acid content. Complex shear modulus (G∗) of the modified asphalts increased both at high and low temperature after incorporating EAA, indicating that EAA could improve the stiffness of asphalt. The drop of tanδ showed the elastic behavior of modified asphalt after modification. Solubility parameter theory and blending theory were selected to explain the bad performance of modified asphalt in storage stability. Adhesive capacity of modified asphalt tended to be better with the increasing of EAA content. Methods to improve the storage stability at high temperature of EAA modified asphalt still remained to be researched in the next.