Coefficient of friction reduction of ethylene‐co‐acrylic acid film: Effects of grafted 12‐aminododecanamide and solvent exposure

The effect of covalently bound 12‐aminododecanamide on the surface coefficient of friction (COF) of ethylene–acrylic acid copolymer (EAA) films was investigated. The reaction involved grafting 12‐aminododecanoic acid to the inherent carboxylic acid groups on the film, followed by amidation of the grafted amino acid. Conversion of film carboxylic acid groups to primary amide groups was also conducted to compare the impact of direct surface amidation. Subsequent measurements showed that both surface amidation schemes reduced the kinetic COF from 0.30 to 0.15 ～ 0.18. Repetitive COF testing revealed that amide‐modified EAA films maintained low COF values that were independent of the number of COF test runs. However, control experiments showed that COF values also depended greatly on simply exposing film to the various reaction solvents, which increased surface roughness. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2242–2248, 2005     

Synthesis,characterization, and antitumor activity of poly(maleic anhydride‐co‐vinyl acetate‐co‐acrylic acid)

The ternary copolymerization of maleic anhydride (MA), vinyl acetate (VA), and acrylic acid (AA) [P(MA‐co‐VA‐co‐AA)], which is considered to be an acceptor–donor–acceptor system, was carried out in 1,4‐dioxane with benzoyl peroxide as an initiator at 70°C under a nitrogen atmosphere. Constants of complex formation for the monomer systems in the study were determined by UV–visible (hydrogen‐bonding complex) and ¹H‐NMR (charge transfer complex) methods, respectively. The results show that polymerization of the P(MA‐co‐VA‐co‐AA) system proceeds by an alternating terpolymerization mechanism. It is shown that the synthesized copolymers have typical polyelectrolyte behavior, ability for reversible hydrolysis–anhydrization reactions, and semicrystalline structures. In these cases, including radical polymerization, and formation of semicrystalline structures, the hydrogen‐bonding effect plays a significant role. The in vitro cytotoxicities of the synthesized terpolymer and alternating copolymer were evaluated using Raji cells (human Burkitt lymphoma cell line). The antitumor activities of prepared anion‐active copolymers were studied using methyl–thiazol–tetrazolium colorimetric assay and 50% of the cytotoxic dose of each copolymer and terpolymer were calculated. Hydrolyzed P(MA‐co‐VA‐co‐AA) and P(MA‐alt‐AA) copolymers have sufficiently high antitumor activity, which depends on the amount of hydrogen‐bonding carboxylic groups and their regular distribution in the side chain of functional macromolecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3425–3432, 2006     

丙烯酸/丙烯酸甲酯共聚物聚合工艺研究及其表征

以丙烯酸(AA)、丙烯酸甲酯(MA)为共聚单体,以过硫酸铵和亚硫酸氢钠为氧化还原体系引发剂,异丙醇为链转移剂,以水为溶剂,采用溶液聚合方法,合成P(AA-MA)共聚物,利用红外光谱对合成的共聚物结构和组成进行表征,研究了各因素对共聚物的特性粘数的影响程度,确定了最佳聚合条件为:单体比例为8∶1,加料时间0.5 h,聚合温度80℃,聚合时间2.5 h,过硫酸铵用量6%,亚硫酸氢钠用量2%,异丙醇100%(以单体质量计)。     

Environmental stability of ethylene–acrylic acid adhesive copolymers bonded to metal substrates

A study was conducted on the influence of high humidity and temperature on aluminum and copper sheet coated with ethylene–acrylic acid or ethylene–methacrylic acid copolymers. Infrared spectrometric and differential thermal analysis data indicate that a contributing cause to failure of the bond between the acrylic acid copolymers and copper is the solubilization of an underlying weak oxide layer under conditions of the test. No significant weakening of the bond of aluminum–adhesive copolymer was observed under high humidity. From oxygen uptake studies, thermogravimetric analysis in air, and infrared spectra of polymer bonded to metals, a general understanding of the thermal-oxidative stability of the ethylene–acrylic and ethylene–methacrylic copolymers has emerged. The acrylic acid copolymers are less stable in an oxidative environment than ethylene homopolymers and the ethylene–alkyl acrylate copolymers.     

Viscoelastic properties of reactive and non‐reactive blends of ethylene‐methyl acrylate copolymers with styrene‐maleic anhydride copolymer

The effects of compatibilizing reactions on the viscoelastic properties and morphology of ethylene‐methyl acrylate copolymers were studied. Potentially reactive blends of styrene‐maleic anhydride copolymer (SMAH) and a terpolymer of ethylene/methyl acrylate/glycidyl methacrylate (E‐MA‐GMA) were compared with a non‐reactive blend of SMAH and an ethylene/methyl acrylate (E‐MA) copolymer with similar rheological properties. Melt mixing was carried out in a batch mixer and in a co‐rotating twin screw extruder. The morphology of the reactive blends showed smaller domain sizes than the non‐reactive blends, and the viscoelastic properties of the blends were very different. The storage and loss moduli and the complex viscosity of the reactive blends were greater than those of non‐reactive blends. The reactive blends had a higher zero shear viscosity, plateau modulus and mean relaxation time than their non‐reactive counterparts, indicating a higher degree of melt elasticity. The melt elasticity was maximum at 25% functionalized ethylene‐methyl acrylate concentration.     

Proton exchange membranes by grafting of styrene–acrylic acid onto FEP by preirradiation technique. I. Effect of synthesis conditions

Grafting of styrene–acrylic acid (sty–AA) polymer onto fluorinated ethylene propylene copolymer (FEP) was carried out by preirradiation of FEP with γ‐rays. Effect of reaction conditions on the degree of grafting such as total radiation dose, monomer concentration, temperature, and time of grafting has been studied. From the study, it is seen that the degree of grafting is strongly dependent on the reaction conditions. The rate dependence of 0.53 (～0.5) and 1.03 (～1) have been obtained with respect to total dose and monomer concentration, respectively indicating that radiation induced grafting follows free radical polymerization. The activation energy for the grafting in the temperature range of 60–90°C is found to be 33 kJ/mol. The results indicate that the grafting takes place by the front mechanism where the grafting starts at surface and slowly proceeds inwards by diffusion of the monomer through the swollen grafted chains. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2572–2577, 2003     

Modification of fast-cure ethylene–propylene diene terpolymer rubber by maleic anhydride and effect of electron donor

Grafting of maleic anhydride (MA) onto fast-cure ethylene–propylene diene terpolymer rubber was studied. The effect of the amount of the MA, initiator (dicumyl peroxide), and electron donor (stearamide) on graft content are described. The potentiometric method and Fourier transform infrared spectroscopy are used to obtained the graft content. The stearamide suppresses the side reactions, such as crosslinking and chain scission. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1–5, 1998     

Radiation-induced Grafting of Acrylic Acid and Vinyl Acetate Monomers onto Heavy-duty Poly(ethylene–vinyl acetate) Films

The preparation of graft films was carried out by direct radiation-induced graft polymerization of acrylic acid and vinyl acetate comonomer onto heavy-duty poly(ethylene–vinyl acetate) films. The effect of various comonomer compositions on the degree of grafting was investigated. The characterization and some selected properties of the graft copolymers prepared were studied. Thermal stability, mechanical and electrical properties of the films showed great promise for some practical applications. © of SCI.     

Preparation and properties of styrene–ethylene–butylene–styrene block copolymer/clay nanocomposites: I. Effect of clay content and compatibilizer types

BACKGROUND: Polymer/clay (silicate) systems exhibit great promise for industrial applications due to their ability to display synergistically advanced properties with relatively small amounts of clay loads. The effects of various compatibilizers on styrene–ethylene–butylene–styrene block copolymer (SEBS)/clay nanocomposites with various amounts of clay using a melt mixing process are investigated. RESULTS: SEBS/clay nanocomposites were prepared via melt mixing. Two types of maleated compatibilizers, styrene–ethylene–butylene–styrene block copolymer grafted maleic anhydride (SEBS‐g‐MA) and polypropylene grafted maleic anhydride (PP‐g‐MA), were incorporated to improve the dispersion of various amounts of commercial organoclay (denoted as 20A). Experimental samples were analyzed using X‐ray diffraction and transmission electron microscopy. Thermal stability was enhanced through the addition of clay with or without compatibilizers. The dynamic mechanical properties and rheological properties indicated enhanced interaction for the compatibilized nanocomposites. In particular, the PP‐g‐MA compatibilized system conferred higher tensile strength or Young's modulus than the SEBS‐g‐MA compatibilized system, although SEBS‐g‐MA seemed to further expand the interlayer spacing of the clay compared with PP‐g‐MA. CONCLUSION: These unusual results suggest that the matrix properties and compatibilizer types are crucial factors in attaining the best mechanical property performance at a specific clay content. Copyright © 2007 Society of Chemical Industry     

Effects of glycerol and ethylene–acrylic acid on composition optimization of PVOH/starch‐blended biodegradable resin using response surface methodology

Response surface methodology was used to analyze the effect of glycerol (X₁) and ethylene–acrylic acid (EAA) level (X₂) on the objective (water solubility index (WSI), water absorption index (WAI), and tensile strength) attributes of a poly(vinyl alcohol) (PVOH)/starch‐blended plastic resin. A rotable central composite design was used to develop models for the objective responses. The experiments were run with different barrel temperatures, such as zone 1: 100°C, zone 2: 100°C, zone 3: 105°C, and zone 4: 105°C, respectively, with a feed rate of 20 g/min and screw speed of 25 rpm. Responses were most affected by changes in glycerol level (X₁) and to a lesser extent by EAA level (X₂). Individual contour plots of the different responses were overlaid, and regions meeting the optimum WSI of 6.10%, WAI of 5.57 g gel/g dry wt, and tensile strength of 62.14 MPa were identified at the glycerol level of 72.41 mL and the EAA level of 36.03 g, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polypropylene/polypropylene‐grafted acrylic acid copolymer/ethylene–Acrylic acid copolymer ternary blends for hydrophilic polypropylene

Ternary blends of polypropylene (PP), a polypropylene‐grafted acrylic acid copolymer (PP‐g‐AA), and an ethylene–acrylic acid copolymer (EAA) were prepared by melt blending. The surfaces of films with different contents of these three components were characterized with contact‐angle measurements. Scanning electron microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis were used to characterize the microstructure, melting and crystalline behavior, and thermal stability of the blends. The contact angles of the PP/PP‐g‐AA blends decreased monotonically with increasing PP‐g‐AA content. With the incorporation of EAA, the contact angles of the PP/PP‐g‐AA/EAA ternary blends decreased with increasing EAA content. When the concentration of EAA was higher than 15 wt %, the contact angles of the ternary blends began to increase. Scanning electron microscopy observations confirmed that PP‐g‐AA acted as a compatibilizer and improved the compatibility between PP and EAA in the ternary blends. Differential scanning calorimetry analysis suggested that acrylic acid moieties could act as nucleating agents for PP in the polymer blends. Thermogravimetric analysis and differential thermogravimetry confirmed the optimal blend ratio for the PP/PP‐g‐AA/EAA ternary blends was 70/15/15. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 436–442, 2006     

Effect of ethylene–acrylate–(maleic anhydride) terpolymer on mechanical properties and morphology of poly(ethylene terephthalate)/polyamide‐6 blends

Background: Poly(ethylene terephthalate) (PET)/polyamide‐6 (PA‐6) blends are promising for engineering and food‐packaging applications. However, their poor toughness limits their use. In this study, an ethylene–acrylate–(maleic anhydride) terpolymer (E‐AE‐MA) was added to PET/PA‐6 blends in order to improve the toughness. Results: Izod impact tests indicated an excellent toughening effect of E‐AE‐MA. E‐AE‐MA particles were observed to be selectively dispersed at the interface between PET and PA‐6 phases and in the domain of the PA‐6 phase. Fourier transform infrared spectroscopy and differential scanning calorimetry results demonstrated that the formation of E‐AE‐MA layers around PA‐6 particles cut off the interaction between PET and PA‐6, resulting in an enlarged PA‐6 phase domain. Conclusion: Based on the experimental results, a core–shell microstructure, with PA‐6 as a hard core and E‐AE‐MA as a soft shell, could be suggested. The formation of this core–shell microstructure, along with the increased PA‐6 phase domain size, is the main toughening mechanism of E‐AE‐MA in PET/PA‐6 blends. Copyright © 2007 Society of Chemical Industry     

Superabsorbent hydrogel of acrylic acid/potassium acrylate copolymers by ultraviolet photopolymerization: Synthesis and properties

Synthesis of superabsorbent hydrogel (SAHG) of acrylic acid‐potassium acrylate copolymer by direct Ultraviolet (UV) photopolymerization is a new method. The effects of degree of neutralization of acrylic acid (AA), photoinitiators, crosslinking agents, and exposure time of UV light on water absorbent properties were investigated. The results showed that the water absorbency (Q) and the salt solution (NaCl, 0.9%) absorbency (Qs) of SAHG, based on Irgacure 651, are high, reaching about 1400 and 130 mL/g, respectively. UV absorption spectrum proved that peak of UV absorption of Irgacure 651 matched the UV light source we used. Among the crosslinking agents, N,N′‐methylene bisacrylamide is more efficient than others, because of its very small content and high Q. ¹³C NMR spectrometry was used to identify the mechanism of crosslinking reaction through esterification of hydroxyethyl acrylate (HEA) and 2‐hydroxypropyl acrylate (HPA) with carboxylic acid group in acrylic acid‐ammonium acrylate copolymerization, but efficiency of crosslinking reaction by esterification was lower than that of copolymerization of vinyl group in crosslinking agent. The Q of acrylic acid‐potassium acrylate copolymer of SAHG reaches 1592 mL/g under the following conditions: degree of neutralization of acrylic acid is 80%, content of Irgacure 651 is 0.25 wt %, content of HEA is 0.2 wt %, and exposure time is 10 min. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1181–1187, 2006     

Preparation and characterization of a methyl methacrylate/ethyl acrylate/acrylic acid terpolymer to improve the homogeneity of ethylene–propylene–diene monomer rubber/poly(vinyl chloride) blends

The emulsion terpolymerization of methyl methacrylate (MMA), ethyl acrylate (EA), and acrylic acid (AA) was carried out under a nitrogen atmosphere at 70°C. The final terpolymer conversion was determined gravimetrically. The synthesized MMA–EA–AA terpolymer was characterized with ¹H‐NMR spectroscopy, thermal analysis, and gel permeation chromatography. Glass‐transition temperatures of the MMA–EA–AA terpolymer were determined with a differential scanning calorimeter. Ethylene–propylene–diene monomer rubber (EPDM)/poly(vinyl chloride) (PVC) blends were prepared with different blend ratios (10/90, 20/80, 30/70, 40/60, and 50/50) in the presence and absence of MMA–EA–AA as a compatibilizer. The morphology of those blends was examined with the aid of a scanning electron microscope. The scanning electron micrographs in the presence of the MMA–EA–AA terpolymer illustrated the disappearance of the macroscale phase separation of EPDM/PVC blends as a result of the incorporation of MMA–EA–AA into that blend, indicating an improvement of the homogeneity. The mechanical properties of the EPDM/PVC blend films and the dielectric properties of the melt blends were investigated. The swelling behavior of the cured blends in the brake fluid was also discussed. The results illustrated that the mechanical properties, the weight swelling values, and the dielectric constant values showed linear behavior versus the blend ratios after the incorporation of the terpolymer. However, those values showed deviations from linearity in the absence of the terpolymer. That, in turn, ensured the results obtained with the scanning electron microscope. The results reveal that the MMA–EA–AA terpolymer prepared can be used successfully to improve the homogeneity of EPDM/PVC blends used in hose and oil seal applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Radiation‐processed polychloroprene‐co‐ethylene–propene diene terpolymer blends: Evaluation of blend morphology,miscibility, and physical properties

The miscibility of polychloroprene rubber (CR) and ethylene–propylene–diene terpolymer rubber (EPDM) was studied over the entire composition range. Different blend compositions of CR and EPDM were prepared by initially mixing on a two‐roll mill and subsequently irradiating to different gamma radiation doses. The blends were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, density measurement, hardness measurement, and solvent permeability analysis. The compatibility of the blends was studied by measuring the glass transition temperature and heat capacity change of the blends. The immiscibility of blends was reflected by the presence of two glass transition temperatures; however, partial miscible domains were observed due to inter diffusion of phases. Permeation data fitted best with the Maxwell's model and indicated that in CR‐EPDM blends, EPDM exists as continuous phase with CR as dispersed phase for lower CR weight fractions and phase inversion occurred in 40–60% CR region. It was observed that CR improved oil resistance of EPDM; however, the effect was prominent for blends of >20% CR content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of new hydrogels on the basis of water‐soluble maleic anhydride copolymers with γ‐aminopropyltriethoxysilane

This work describes the synthesis and macromolecular reactions of maleic anhydride (MA)–acrylic acid (AA) binary reactive copolymers with γ‐aminopropyltriethoxysilane (APTS) as a polyfunctional crosslinker. Copolymers with a given composition of MA–AA (47.17–52.83 wt %) were synthesized by radical binary copolymerization with benzoyl peroxide as an initiator in p‐dioxane at 70°C in nitrogen atmosphere and initial monomer ratio of 1 : 1. It is shown that the network structure is formed in MA–AA/APTS in water by intermolecular reaction between the anhydride unit and the amine group, as well as between the etoxysilyl fragment and free carboxyl groups of the acrylic acid and maleic anhydride unit. Swelling parameters such as beginning time of hydrogel formation, initial rate of swelling, swelling rate constant, equilibrium swelling, and equilibrium water content were determined for copolymer/APTS/water systems with various copolymer/crosslinker ratios. Formation of a hyperbranched network structure through the fragmentation of side‐chain reactive groups in the studied systems was confirmed by FTIR, TGA, and DSC methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4009–4015, 2003     

Swelling behavior and determination of diffusion characteristics of acrylamide–acrylic acid hydrogels

In this study, a random copolymer of acylamide and acrylic acid [poly(AAm‐co‐AA)] was prepared by a redox copolymerization method of their aqueous solutions. The effects of initial AAm/AA mole ratio, PEG 4000 content, and N,N′‐methylenebisacrylamide concentration on swelling behavior were investigated in water. Average molecular weights between crosslinks, percentage swelling, swelling equilibrium values, and diffusion/swelling characteristics (i.e., the structure of network constant, the type of diffusion, the initial swelling rate, swelling rate constant) were evaluated for every hydrogel systems. The hydrogels showed mass swelling capabilities in the range 789–1040% (for AAm/AA hydrogels), 769–930% (for AAm/AA hydrogels in the presence of PEG 4000), and 716–1040% (for AAm/AA hydrogels containing different concentrations of the crosslinker). The swelling capabilities of the hydrogels decreased with the increasing AA, PEG 4000, and crosslinker concentrations. The diffusion of water into AAm/AA hydrogels was found to be a non‐Fickian type. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1289–1293, 2004     

Synthesis of silicone–acrylic resins and their applications to superweatherable coatings

Silicone–acrylic resins were synthesized to prepare superweatherable paints for building materials. The raw materials used were n‐butyl acrylate, methyl methacrylate, and n‐butyl methacrylate as acrylic monomers and 3‐methacryloxypropyltrimethoxysilane (MPTS) as a silicone monomer reactive with the acrylic monomers. Acrylic copolymers were synthesized such that their glass‐transition temperatures were adjusted to 30°C and their MPTS contents were varied to 10, 20, and 30 wt %. As the content of silicone and MPTS increased, average molecular weight and viscosity increased, and thermal stability at high temperatures improved. When we tested the properties of coatings by blending the synthesized silicone–acrylic resins with a white pigment, adhesion was superior with various substrates, and their properties were suitable on the whole. Weatherability was tested by an outdoor exposure test with a weather‐ometer and an accelerated weathering tester, and their results showed that silicone–acrylic resin composed of 30 wt % MPTS was a superweatherable coating. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1614–1623, 2001     

Synthesis of nanosized ethylene–propylene rubber latex via polyisoprene hydrogenation

Nanosized ethylene–propylene rubber (EPM) latex with a particle size of 47 nm was synthesized via an alternative route consisting of isoprene (IP) polymerization followed by hydrogenation. First, the IP monomer was polymerized by differential microemulsion polymerization to obtain polyisoprene (PIP) rubber latex with a particle size of 42 nm. The structure of synthetic PIP was hydrogenated at the carbon–carbon double bonds to produce an ethylene–propylene copolymer by diimide reduction in the presence of hydrazine and hydrogen peroxide using boric acid as promotor. The degree of hydrogenation was determined by proton nuclear magnetic resonance (¹H‐NMR) spectroscopy and the structure of the ethylene–propylene copolymer was identified by ¹³C‐NMR spectroscopy. In nanosized PIP hydrogenation, the hydrogenation level was found to be increased by boric acid addition. An EPM yield of 94% was achieved using a hydrogen peroxide : hydrazine ratio of 1.5 : 1. The EPM produced from PIP has high thermal stability with the maximum decomposition temperature of 510°C and a glass transition temperature of ‐42.4°C close to commercial ethylene–propylene diene rubber. Dynamic mechanical analysis indicated that EPM had a maximum storage modulus due to the saturated carbons domains of the ethylene segments in the polymer chains. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Kinetic study of acrylic monomer grafting in the presence of a polyfunctional monomer onto radioperoxided poly(ethylene–tetrafluoroethylene) copolymer

Acrylic acid (AA), methacrylic acid (MA) and diethyleneglycol dimethacrylate (DEGDM) are grafted onto 100 μm radioperoxided poly(ethylene–tetrafluroethylene) copolymer (ETFE). The influences of the homopolymerization inhibitor, the solvent, the grafting temperature, and the monomer content on the grafting kinetics are studied. For the grafting of acrylic monomers, the limitation of the grafting yield is more important for AA grafting whatever the nature of the metallic salt; the difference between the two homopolymerization inhibitors is their respective concentration to obtain a given grafting yield. For the AA + DEGDM cografting, the grafting yield increases with the DEGDM content of the grafting solution. In both cases, the overall activation energy has been calculated, and its variation as a function of the composition of the grafting solution is discussed. © 1994 John Wiley & Sons, Inc.