Surface and interfacial FTIR spectroscopic studies of latexes. IX. The effect of homopolymer and copolymer structures on surfactant mobility in Sty/BA latices

The effects of homopolymer and copolymer compositions and structures in styrene/n-butyl acrylate (Sty/BA) latices on sodium dioctyl sulfosuccinate (SDOSS) surfactant mobility and its preferential concentration at the film–air (F–A) and film–substrate (F–S) interfaces were examined using attenuated total reflectance Fourier transform infrared (ATR FTIR) spectroscopy. It appears that the SDOSS concentration at the F–S interface is highest when the Sty/BA feed ratio is 50/50, and the excess of Sty results in migration of SDOSS surfactant to the F–A interface. This behavior is attributed to the increased glass transition temperature and diminished compatibility between surfactant molecules and copolymer latex. This study also shows that the primary factors that influence exudation to either F–A or F–S interfaces are surface tension of the substrate, glass transition temperature, water flux during coalescence, and compatibility between latex components. © 1995 John Wiley & Sons, Inc.     

Surface and interfacial FTIR spectroscopic studies of latexes. I. Surfactant–copolymer interactions

Molecular level interactions between surfactants and copolymers as well as transient effects during latex film formation play an important role in latex technology. Photoacoustic (PA) and attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy were utilized for the characterization of interactions between sodium dioctylsulfosuccinate and ethyl acrylate/methacrylic acid (SDOSS/EA/MAA) copolymer in latex films at both the film–air and film–substrate interfaces. It is shown that the splitting of the asymmetric S? O stretching normal vibrations of the SO groups in the presence of Na⁺ counterions occurs only when weak ? COOH acid groups of latex are present. The absence of the COOH groups either by neutralization of latex or intentional synthesis eliminates the S? O···H? O? associations that are the primary source of the symmetry changes resulting in the splitting of the S? O symmetric mode at 1050 cm^?1 to two bands at 1046 and 1056 cm^?1.     

Surface and interfacial FTIR spectroscopic studies of latexes. XI. The effect of Sty/n-BA copolymer composition on the orientation of SDOSS surfactant molecules

These studies examine how various latex copolymer compositions, ranging from 100% n-BA to 50%/50% Sty/n-BA, may influence sodium dioctylsulfosuccinate (SDOSS) mobility, diffusion, and orientation near the film–air (F–A) and film–substrate (F–S) interfaces. Polarized attenuated total reflection Fourier transform infrared spectroscopy is utilized to examine the surfactant behavior in Sty/n–BA latexes at the F–A and F–S interfaces. Based on the analysis developed for the purpose of these studies, the highest concentration of SDOSS is detected near the F–A interface for 50%/50% Sty/n-BA compositions. However, when the content of styrene in Sty/n-BA compositions. However, when the content of styrene in Sty/n-BA copolymer is diminished, the highest content of SDOSS is detected near the F–S interface. This behavior is particularly evident for 100% poly(n-BA) latexes. When SDOSS molecules are near the F–A and F–S interfaces, the SO₃⁻Na⁺ hydrophilic ends are preferentially parallel to the surface, whereas hydrophobic tails are perpendicular. © 1996 John Wiley & Sons, Inc.     

Surface and interfacial FT–IR spectroscopic studies of latexes. VIII. The effect of particle and copolymer composition on surfactant exudation in styrene-n-butyl acrylate copolymer latex films

Polarized attenuated total reflection Fourier transform infrared (ATR FT–IR) spectroscopy was used to identify the mobility and surfactant exudation of sodium dioctyl sulfocuccinate (SDOSS) surfactant molecules to the film–air (F–A) and film–substrate (F–S) interfaces in styrene/n-butyl acrylate (Sty/n-BA) latex films. It was found that, depending upon the latex particle composition, the surfactant molecules could be driven to the F–A or F–S interfaces. The primary factors that governed the direction of exudation were the compatibility of the latex components, interfacial film-substrate surface tension, and the chemical composition of the latex particles. Concentration, as well as orientation, of the hydrophilic SONa⁺ surfactant ends changed as a function of depth and the latex particle composition. © 1993 John Wiley & Sons, Inc.     

Surface and interfacial fourier transform infrared spectroscopic studies of latexes. XIV. Surface phase separation in polystyrene/poly-n-butyl acrylate latex films

This study focuses on the behavior of sodium dioctylsulfosuccinate (SDOSS) in 50/50 w/w % polystyrene/poly(butyl acrylate) (p-Sty/p-BA) latex films. Specifically, mobility and orientation are examined in the context of the film formation by the use of dynamic mechanical thermal analysis and attenuated total reflectance (ATR) Fourier transform infrared (FT-IR) spectroscopy. While for the homopolymer blends of p-Sty and p-BA, two T_g values resulting from a phase separation of p-Sty and p-BA phases are observed, only a single T_g is detected for a copolymer of the same mixture, indicating a single phase within the film. ATR FTIR spectroscopic data indicate that the phase separation of p-Sty and p-BA blends does not occur uniformly across the film. After coalescence, p-Sty particles produce a significant degree of stratification at approximately 1.6 μm from the film surface. At this depth, the polystyrene rings assume preferentially parallel orientation to the film surface. At the same time, the hydrophilic groups of SDOSS surfactant (SO⁻₃Na⁺) are oriented preferentiallyparallel to the surface. Under high relative humidity conditions, water is able to diffuse into the film and swells the surface layers, thus causing them to expand. As a result, the top, predominately poly-n-BA surface becomes “thicker», and p-Sty phase appears to be near 2.3 μm from the surface. The polystyrene rings maintain their preferential parallel orientation to the surface, but the hydrophilic groups of SDOSS are able to diffuse into the film with the water uptake and are thus not present at the filmair interface. © 1996 John Wiley & Sons, Inc.     

Surface and interfacial FTIR spectroscopic studies of latexes. II. Surfactant–copolymer compatibility and mobility of surfactants

Whereas molecular level interactions between sulfonate groups of SDOSS surfactant and COOH groups of EA/MMA copolymer have been discussed in part I of this series, the major focus of this work is to establish the effect of compatibility on the distribution of surfactants at the film–air and the film–substrate interfaces. It is found that the exudation of anionic surfactants is inhibited in neutralized ethyl acrylate/methacrylic acid latex films. On the other hand, nonionic surfactants do not exhibit enrichment at the film interfaces. The inhibited exudation of anionic surfactants is attributed to the increased compatibility resulting from surfactant penetration into the swollen latex particles. This is followed by the formation of solubilized polymer–surfactant complexes through the adsorption of surfactant onto the hydrophobic polymer segments. The effect of neutralization of the carboxylic acid groups on the exudation of anionic surfactants suggests the formation of hydrophobic interactions that overwhelm surface tension effects and prevent surfactant enrichment at either interface.     

Surface and interfacial fourier transform infrared spectroscopic studies of latexes. XVI. Quantitative analysis of surfactant in multilayered films

Migration and concentration levels of sodium dioctylsulfosuccinate (SDOSS) surfactant molecules in 50%/50% styrene/butyl acrylate latex were detected at the film-substrate (F-S) and film-air (F-A) interfaces in mono- and double-layered films. For the purpose of quantitative analysis, absorption coefficients of the 1,056 and 1,046 cm⁻¹ bands attributed to the SO₃⁻Na⁺…HOOC and SO⁻₃Na⁺…H₂O associations, respectively, were determined. Using group theory formalism, local geometries of the SO⁻₃Na⁺ hydrophilic groups of SDOSS can be predicted. The analysis is extended to the 1,261 and 1,209 cm⁻¹ bands resulting from the S—O asymmetric stretching vibrations, due to the same SO⁻₃Na⁺ … HOOC and SO⁻₃Na⁺ … H₂O associations, and to the 1,290 and 1,236 cm⁻¹ bands, due to asymmetric stretching modes of hydrophobic tails of the SDOSS. By the use of polarization attenuated total reflectance Fourier transform infrared (ATRFT-IR) experiments, these studies show that hydrophilic SO⁻₃Na⁺ ends on SDOSS are preferentially parallel to the film surface. At the same time, hydrophobic tails are perpendicular to the surface. The assessment of the amounts of SDOSS at the F-S and F-A interfaces was obtained by quantitative ATR FTIR analysis, which was extended to the silicone-modified double-layer latex films. In this case, the concentration of SDOSS molecules decreases as the depth of penetration increases. The highest concentrations of SDOSS molecules are detected at the shallowest depths near the surface of the top layer and the interfacial regions between the latex layers. © 1996 John Wiley & Sons, Inc.     

Influence of spacer groups on grafting ability,curing ability,and film properties of water-based radiation curable latexes

Film-forming polystyrene/poly(n-butyl acrylate-co-glycidyl methacrylate) [PS/P(BA-co-GMA)] core–shell latex particles were prepared via a two-stage emulsion polymerization procedure using a PS latex seed. A delayed addition of GMA was used to locate the functional epoxy groups near the surface of the particles. The surface-bound epoxy groups were used as grafting sites for unsaturated carboxyl functional monomers having the unsaturated groups and the carboxylic group separated by 1, 5, or 10 oxyethylene units. Grafting and curing characteristics and film properties after irradiation were investigated as a function of the number of oxyethylene units. A BA-GMA [P(BA-co-GMA)] copolymer was used as a model system for the core–shell latex particles for quantification of the grafting reactions. The grafting was demonstrated by FTIR and ¹H-NMR spectroscopy. The effects of crosslinking was studied by thermal mechanical analysis and dynamical mechanical analysis. Differential photocalorimetry was also used for evaluation of the curing ability. It was demonstrated that the reagent having five oxyethylene units in the spacer group was grafted onto the polymer backbones to a larger extent than the other two reagents, and a more thoroughly cured film was obtained upon irradiation. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 897–906, 1998     

Surface and interfacial fourier transform infrared spectroscopic studies of latexes. XV. Orientation of the sodium dioctyl sulfosuccinate surfactant molecules in core/shell-type styrene/butyl acrylate latex films at the film–air and film–substrate interfaces

This study addresses the effect of particle structure and composition on the mobility and orientation of sodium dioctyl sulfosuccinate (SDOSS) surfactant molecules in polybutyl acrylate/polystyrene core/shell-type latex films near the film-air (F-A) and film-substrate (F-S) interfaces. In an effort to determine how the surface tension of the substrate influences the migration and orientation of the SDOSS surfactant molecules, polytetrafluoroethylene (PTFE) and liquid Hg substrates were used. It appears that, as the concentration of styrene monomer in the latex increases, SDOSS migrates toward the F-A and F-S interfaces. As the surface tension of the substrate changes from 18 mN/m in PTFE to 400 mN/m for liquid Hg, the surfactant also migrates toward the two interfaces. For the latex particles composed of 50%/50% styrene/n-butyl acrylate (Sty/n-BA) latex copolymer, the hydrophilic SO⁻₃Na⁺ groups of SDOSS surfactant are present primarily near the F-A interface, and they appear to be mostly parallel to the surface for the films cast on the PTFE surface. For the latex films cast on the liquid Hg surface, the SDOSS hydrophilic surfactant groups are found to be preferentially parallel near the F-A interface and perpendicular near the F-S interface. These studies indicate that the surfactant concentration and its orientation throughout the latex film change as a function of the initial monomer composition and the surface tension of the substrate. Furthermore, the SDOSS concentration appears to vary with depth into the latex interfaces. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of urethane/acrylate composite latex

Polyurethane dispersion and urethane/acrylate composite latex were synthesized and characterized by using a particle size analyzer, gel permeation chromatograph (GPC), Fourier transform infrared spectroscopy coupled with attenuated total reflectance (FTIR‐ATR), dynamic mechanical analysis (DMA), and instron test machine. The amount of solvent and dimethylolpropionic acid (DMPA) used during synthesis of polyurethane resin straightway affected the average particle size and stability of aqueous polyurethane dispersion. The particle size of polyurethane dispersion had nothing to do with that of composite latex. FTIR‐ATR analyses displayed both air‐facing and substrate‐facing surfaces, containing more polyurethane component than the average composition. Some crosslinking reactions occurred in preparing urethane/acrylic composite latex, as indicated by FTIR analyses and solvent extraction. DMA demonstrated three glass transitions for the film from composite latex. Instron tests exhibited better film performance properties for the composite latex than for the corresponding blend latex. A possible particle growth mechanism for preparing urethane/acrylate composite latex was proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1620–1628, 2002; DOI 10.1002/app.10526     

Surface and interfacial FT–IR spectroscopic studies of latexes. VI. Orientation and spatial distribution of acid functionalities at the film–substrate interface

Formation of dimeric carboxylic acid functional groups observed at the film-substrate interface of ethyl acrylate/methacrylic acid (EA/MAA) and butyl acrylate / methyl meth-acrylate / methacrylic acid (BA/MMA/MAA) latex films prepared on a high surface tension substrate, such as liquid mercury, is observed when sodium dioctyl sulfosuccinate (SDOSS) is employed as the synthetic emulsifier. To address the acid species assembled at this interface due to the inability of SDOSS to effectively alleviate interfacial tension and to assess the orientation and spatial configuration of acid groups species at the interface, polarized attenuated total reflectance, Fourier-transform infrared spectroscopy (ATR FT–IR) is employed. It is found that the acid dimer rings adopt an average “on-edge” configuration at the interface with the hydrogen-bonded rings perpendicular to the film-mercury interface. This configuration serves to provide not only the necessary interfacial acid-dimer layer, but also facilitates favorable ring–ring interactions between groups of opposite polarity on adjacent rings. This study indicates that the on-edge configuration may also serve to reduce unfavorable interactions between the polar acid functionality and the less polar components present in the bulk of the coalesced latexes. © 1993 John Wiley & Sons, Inc.     

Green preparation and physical properties of maleated sulfur-prevulcanized natural rubber

The maleated sulfur-prevulcanized natural rubber (M-SPNR) was prepared from grafting maleic anhydride (MA) onto SPNR latex particle by using benzoyl peroxide as an initiator. Natural rubber latex particle was vulcanized first, and then it was maleated to M-SPNR. The average particle size of M-SPNR was greater than that of SPNR possibly due to the formation of aggregate after addition of MA. The symmetric (strong) and asymmetric (weak) carbonyl stretching vibrations of succinic anhydride rings were confirmed by ATR–FTIR at 1,780–1,784 and 1,854?cm^?1, respectively. The swelling ratios of M-SPNR latex film decreased with increasing MA contents. The tensile strength, modulus, hardness, and elongation at break of SPNR latex film dramatically increased after grafting with MA. Due to the reduction of double bond, the thermal stability of M-SPNR film was better than that of SPNR. The environmental friendly M-SPNR would be further applied as a compatibilizer between NR and biopolymer.     

Surface and interfacial FTIR spectroscopic studies of latexes. IV. The effect of surfactant structure on the copolymer–surfactant interactions

The interactions between sodium dodecylbenzene sulfonate (SDBS) and the components of an ethyl acrylate/methacrylic acid (EA/MAA) copolymer latex were examined and the influences of using D₂O as the synthetic suspension medium were investigated. Whereas it is found that D₂O has no detectable influence on the fully coalesced latex films, the film coalescence conditions are shown to significantly affect the nature of surfactant interactions within the film matrix. When films are prepared and stored under controllable low atmospheric water-vapor concentrations, hydrogen-bonding interactions between the surfactant SO₃^?Na⁺ groups and the copolymer acid functionality dominate. However, coalescence and storage of the films under higher relative humidity conditions results in a displacement of these interactions in favor of the hydrated form of the surfactant. It is also shown that the presence of an aromatic ring adjacent to the surfactant sulfonate group exerts an influence on the nature of the SO₃^? ··· HOOC interactions within the copolymer matrix. Relative to sodium dioctyl sulfosuccinate (SDOSS), the aromatic group near hydrophilic end of SDBS increases the strength of the S? O bond in the presence of acid interactions. © 1993 John Wiley & Sons, Inc.     

Synthesis and properties of fluorine–silicon modified polyacrylate hybrid latex particles with core–shell structure obtained via emulsifier‐free emulsion polymerization

A core–shell fluorine–silicon modified polyacrylate hybrid latex was successfully prepared via emulsifier‐free emulsion polymerization. The chemical composition and core–shell morphology of the resultant hybrid particles were investigated using ¹H NMR and Fourier transform infrared spectroscopies and transmission electron microscopy (TEM), respectively. TEM analysis indicated that the core–shell hybrid particles were uniform with narrow size distributions. The particle size and zeta potential decreased with an increase of alkylvinylsulfonate surfactant from 2.5 to 6.0 wt%. X‐ray photoelectron spectroscopy revealed that fluorine concentrated preferentially at the film surface during a film‐formation process. The film formed from the fluorine–silicon modified polyacrylate showed much higher thermal stability than a film formed from polyacrylate and fluorine‐modified polyacrylate. Contact angle results showed that a finished fabric had remarkable water repellency. © 2015 Society of Chemical Industry     

Preparation and surface properties of core‐shell polyacrylate latex containing fluorine and silicon in the shell

The core‐shell polyacrylate latex particles containing fluorine and silicon in the shell were successfully synthesized by a seed emulsion polymerization, using methyl methacrylate (MMA) and butyl acrylate (BA) as main monomers, dodecafluoroheptyl methacrylate (DFMA), and γ‐(methacryloxy) propyltrimethoxy silane (KH‐570) as functional monomers. The influence of the amount of fluorine and silicon monomers on the emulsion polymerization process and the surface properties of the latex films were discussed, and the surface free energy of latex films were estimated using two different theoretical models. The emulsion and its films were characterized by particle size distribution (PSD) analysis, transmission electron microscopy (TEM), Fourier transform infrared spectrum (FTIR), nuclear magnetic resonance (¹H‐NMR and ¹⁹F‐NMR) spectrometry, contact angle (CA) and X‐ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetry (TG) analysis. The results indicate that the average particle size of the latex particles is about 160 nm and the PSD is narrow, the synthesized latex particles exist with core‐shell structure, and a gradient distribution of fluorine and silicon exist in the latex films. In addition, both the hydrophobicity and thermal stability of the latex films are greatly improved because of the enrichment of fluorine and silicon at the film‐air interface, and the surface free energy is as low as 15.4 mN/m, which is comparable to that of polytetrafluoroethylene (PTFE). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fluorinated polymers as stone‐protective materials: an FTIR study on intermolecular interactions

Attempts have been performed to obtain spectroscopic evidence of intermolecular interactions between fluorinated polymers to be used as protective materials and various stones. In this paper we report an investigation by means of FTIR spectroscopy on poly(vinyl fluoride)(PVF) which contains acid hydrogens that can give rise to intermolecular interactions with calcium carbonate. Spectral changes have been found in the C? H and C? F stretching regions at 3000–2840 and 1200–950 cm^?1, respectively. These last are attributed to intermolecular interactions of the polymer with CO₃^2? and with conformational changes of the macromolecular chain. Scanning electron microscopy investigations were also performed on marble slabs coated with a PVF film in order to gain information about the morphology of the polymer film. Copyright © 2004 Society of Chemical Industry     

Multi-walled carbon nanotube reinforced self-crosslinking hydrogenated carboxylated nitrile butadiene rubber latex film with improved properties

A dielectric self-crosslinking hydrogenated carboxylated nitrile butadiene rubber (HXNBR) latex film was prepared by diimide reduction hydrogenation of XNBR latex and the doping of multi-walled carbon nanotube (MWCNT). The structures of the HXNBR and XNBR were characterised by Fourier transform infrared spectroscopy (FTIR) and ¹HNMR, confirming the successful hydrogenation of XNBR. The mechanical, thermal, and electrical properties of the prepared HXNBR latex films were studied, and the HXNBR latex film reinforced by only 3?phr MWCNTs exhibited improved mechanical, thermal, and dielectric properties.     

Investigation of fluorinated polyacrylate latex with core–shell structure

Fluorinated polyacrylate latices with core–shell structure were prepared by semi‐continuous emulsion polymerization, using a mixed emulsifier system composed of a reactive emulsifier and a small amount of anionic emulsifier. The conversion and chemical components of the final latices were studied by gravimetric methods and Fourier‐transform infrared (FTIR) spectrometry, respectively. The structure of the latex particles was determined by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and particle size analysis. The latex films exhibited a low surface energy and high water‐contact angles. The surface analysis from X‐ray photoelectron spectroscopy (XPS) revealed that the fluorinated components preferentially self‐organized at the film–air interface. From XPS depth profiling of the film, it was found that a gradient concentration of fluorine existed in the structure of the latex film from the film–air interface to the film–glass interface. Compared with the core–shell structure with a fluorinated core, the core–shell structure with a fluorinated shell was more effective for modifying the properties of the latex films. Copyright © 2005 Society of Chemical Industry     

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

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

Ultraviolet and infrared spectral analysis of irradiated polyethylene films: Correlation and possible application for large-dose radiation dosimetry

A detailed study was performed to develop the dosimetric characteristics of commercial low-density polyethylene film (LDPE), which is, by far, the most commonly used plastic for food and for many other-purpose packaging film, to be used as a film dosimeter for large-dose γ-radiation dosimetry. The useful dose range extends up to 880 kGy. Correlations were established between the absorbed dose of γ-radiation and the radiation-induced changes in LDPE measured using Fourier transform infrared (FTIR) and ultraviolet (UV) spectrophotometry. The results showed a significant dependence of the response on the selected readout tool of measurements whether FTIR (at 1716 cm⁻¹) or UV (at 220 and 270 nm) as well as on the quantity used for calculation. The radiation-chemical yield of the ketonic carbonyl group produced in irradiated LDPE film was found to be 0.7 μmol/J. The assessment of the random uncertainty associated with the measurement of the dose response and the effect of relative humidity during irradiation on the dosimeter performance as well as the postirradiation stability at different storage conditions are discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1837–1851, 1998