Development and characterization of reactive extruded PVC/polyacrylate blends

This paper describes a method to obtain polymer blends by the absorption of a liquid solution of monomer, initiator, and a crosslinking agent in suspension type porous poly(vinyl chloride) (PVC) particles, forming a dry blend. These PVC/monomer dry blends are reactively polymerized in a twin‐screw extruder to obtain the in situ polymerization in a melt state of various blends: PVC/poly(methyl methacrylate) (PVC/PMMA), PVC/poly(vinyl acetate) (PVC/PVAc), PVC/poly(butyl acrylate) (PVC/PBA) and PVC/poly(ethylhexyl acrylate) (PVC/PEHA). Physical PVC/PMMA blends were produced, and the properties of those blends are compared to reactive blends of similar compositions. Owing to the high polymerization temperature (180°C), the polymers formed in this reactive polymerization process have low molecular weight. These short polymer chains plasticize the PVC phase reducing the melt viscosity, glass transition and the static modulus. Reactive blends of PVC/PMMA and PVC/PVAc are more compatible than the reactive PVC/PBA and PVC/PEHA blends. Reactive PVC/PMMA and PVC/PVAc blends are transparent, form single phase morphology, have single glass transition temperature (T_g), and show mechanical properties that are not inferior than that of neat PVC. Reactive PVC/PBA and PVC/PEHA blends are incompatible and two discrete phases are observed in each blend. However, those blends exhibit single glass transition owing to low content of the dispersed phase particles, which is probably too low to be detected by dynamic mechanical thermal analysis (DMTA) as a separate T_g value. The reactive PVC/PEHA show exceptional high elongation at break (～90%) owing to energy absorption optimized at this dispersed particle size (0.2–0.8 µm). Copyright © 2005 John Wiley & Sons, Ltd.     

Structure formation of PVDF/PMMA blends studied

Conformational formation and crystallization dynamics of miscible PVDF/at-PMMA and PVDF/iso-PMMA polymer blends from the molten state were studied by the simultaneous DSC/FT-IR measurement. Formation of TGTG' conformation occurred before starting crystallization exothermic peak in the PMMA content (_PMMA) range from 0 to 0.4 for both blends. The formation rate of TGTG' conformation, crystal growth rate and surface free energy of PVDF crystal in blends depended linearly on _PMMA for PVDF/at-PMMA, however, those rates for PVDF/iso-PMMA slightly influenced by _PMMA. These results suggested that the former was miscible blend in molecular level, however, the latter was a miscible blend with large concentration fluctuation or a partially segregated system.     

s-Triazine containing flame retardant hyperbranched polyamines: Synthesis, characterization and properties evaluation

A s-triazine containing hyperbranched polyamine (HBPA) has been synthesized from cyanuric chloride and aromatic diamine, 4,4′-(1,4-phenylenediisopropylidene) bis-aniline by nucleophilic displacement polymerization technique using an A₂ + B₃ approach with high yield (>80%). The synthesized polymer has been characterized by ¹H NMR, ¹³C NMR, FT-IR spectroscopic studies, elemental analysis, solubility and measurement of solution viscosity. The thermogravimetric (TG) analysis and differential scanning calorimetric (DSC) studies indicate that the polymer is thermostable upto 290 °C without any decomposition and has glass transition temperature of 243 °C. The flame retardancy of the pure powder polymer and the blends with linear commercial polymers such as plasticized PVC and LDPE with this hyperbranched polymer were investigated by the measurement of limiting oxygen index (LOI) value. The results show that the polymer has self-extinguishing characteristic (LOI = 38) and acts as an effective flame retardant additive for the above linear base polymers. The synergistic effect of this hyperbranched flame retardant was observed with triphenyl phosphine oxide in the same base polymers. The flammability efficiency of the hyperbranched polyamine is also evaluated by help of thermogravimetric (TG) analysis. The heat aging and leaching in different chemical media did not influence the flame retardancy of the blends.     

Using near-infrared overtone regions to determine biodiesel content and adulteration of diesel/biodiesel blends with vegetable oils

This work evaluates the use of near-infrared (NIR) overtone regions to determine biodiesel content, as well potential adulteration with vegetable oil, in diesel/biodiesel blends. For this purpose, NIR spectra (12,000–6300 cm⁻¹) were obtained using three different optical path lengths: 10 mm, 20 mm and 50 mm. Two strategies of regression with variable selection were evaluated: partial least squares (PLS) with significant regression coefficients selected by Jack-Knife algorithm (PLS/JK) and multiple linear regression (MLR) with wavenumber selection by successive projections algorithm (MLR/SPA). For comparison, the results obtained by using PLS full-spectrum models are also presented. In addition, the performance of models using NIR (1.0 mm optical path length, 9000–4000 cm⁻¹) and MIR (UATR – universal attenuated total reflectance, 4000–650 cm⁻¹) spectral regions was also investigated. The results demonstrated the potential of overtone regions with MLR/SPA regression strategy to determine biodiesel content in diesel/biodiesel blends, considering the possible presence of raw oil as a contaminant. This strategy is simple, fast and uses a fewer number of spectral variables. Considering this, the overtone regions can be useful to develop low cost instruments for quality control of diesel/biodiesel blends, considering the lower cost of optical components for this spectral region.     

Electrical and structural analysis of conductive polyaniline/polyacrylonitrile composites

Conducting composites of polyacrylonitrile (PAN) copolymer containing 10% mass ratio methylacrylate and dodecylbenzene sulfonic acid doped polyaniline (PANI-DBSA) were prepared by solution blending. Electrical properties of the blends were characterized by means of electrical conductivity measurements and the phase structures were investigated via scanning electron microscopy (SEM), X-ray diffraction (XRD), FT-IR spectroscopy, differential scanning calorimetry (DSC) and dynamical mechanical analysis (DMA). It was found that the electrical conductivity of the composites increased with the increase of PANI-DBSA content and the percolation threshold lay around 3.2 wt%. DSC and DMA measurements showed that there was only one T_g for each blend and the values of T_g varied with the PANI-DBSA content, implying that the PANI-DBSA/PAN blend was at least partially compatible. The formation of the hydrogen bonding between the carbonyl groups in PAN copolymer and the imine groups in PANI-DBSA was identified by the FT-IR spectra. XRD demonstrated that the intrinsic layered arrangement of PANI-DBSA was disaggregated in the blends. Nanosize network structure of PANI-DBSA dispersing in PAN matrix and the so-called phase reverse occurring in the skin layer of the film samples at low PANI-DBSA loading were observed by SEM.     

Raman and Wide-Angle X-Ray Diffraction Studies on Molecular Structure,Crystallinity, and Morphology of Uncompatibilized and Compatibilized Blends of High Molecular Weight Polyethylene/Nylon 12

Molecular structure, crystallinity and morphology of uncompatibilized and compatibilized blends of high molecular weight polyethylene (HMWPE) and Nylon 12 were investigated by using Fourier-transform (FT) Raman spectroscopy, wide-angle x-ray diffraction (WAXD), and scanning electron microscopy (SEM). One of the important purposes of the present study is to compare the present results for HMWPE/Nylon 12 with the previously obtained results for high-density polyethylene (HDPE/Nylon 12). Uncompatibilized and compatibilized blends of HMWPE/Nylon 12 with a Nylon 12 content ranging from 10 to 90 wt% at increments of 10 wt% were prepared. The compatibilized polymer blends were prepared by adding a small amount of maleic anhydride (MAH), and SEM images show that the addition of the small amount of MAH (0.5 wt%) yields a marked improvement of dispersion of HMWPE and Nylon 12. To evaluate the crystallinity of HMWPE from Raman spectra, the relative intensities of bands at 1418 and 1129 cm⁻¹ to the intensity of a band at 1000 cm⁻¹ (I₁₄₁₈/I₁₀₀₀ and I₁₁₂₉/I₁₀₀₀) were estimated for all the uncompatibilized and compatibilized blends of HMWPE/Nylon 12. From the comparison of the relative intensities (I₁₄₁₈/I₁₀₀₀ and I₁₁₂₉/I₁₀₀₀) between the uncompatibilized and compatibilized blends of HMWPE/Nylon 12 it was found that when the Nylon 12 content reaches 40 wt% the crystallinity of HMWPE in the compatibilized blends becomes higher than that of HMWPE in the uncompatibilized blends. The uncompatibilized and compatibilized blends of HMWPE/Nylon 12 (50/50) show quite different x-ray diffraction patterns; the compatibilized blend shows a significantly larger orientational effect in the x-ray pattern of HMWPE. It seems that the increase of interaction of MAH-HMWPE with the Nylon 12 matrix leads to the additional crystallinity.     

Flory-huggins interaction parameters of LCP/thermoplastic blends measured by DSC analysis

Liquid crystalline polymer/polyamide 66 (LCP/PA66) and LCP/poly(butyl terephthalate) (LCP/PBT) blends were compounded using a Brabender Plasticorder equipped with a mixing chamber. The LCP employed was a semi-flexible liquid crystalline copolyesteramide based on 30 mol% of p-amino benzoic acid (ABA) and 70 mol% of poly(ethylene terephthalate) (PET). The Flory-Huggins interaction parameters (χ12) of the LCP/ PA66 and LCP/PBT blends are estimated by melting point depression from DSC measurement. The results indicate that c12 values all are negative for LCP/PA66 and LCP/PBT blends, and when the LCP content in these blends is more than 10 mass%, the absolute value of χ₁₂ decreases. Thereby, we can conclude that LCP/PA66 and LCP/PBT blends are fully miscible in the molten state, the molecular interaction between the LCP and PA66 is stronger than that between LCP and PBT. As the LCP content in LCP/PA66 and LCP/PBT blends is more than 10 mass%, the molecular interaction between LCP and matrix polymer decreases. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electrochemical characterization of plasticized polymer electrolytes based on ABS/PMMA blends

Electrochemical characteristics of plasticized polymer electrolytes based on poly(acrylonitrile-butadene-styrene) and poly(methyl methacrylate) (abbreviated as ABS/PMMA) blends have been studied. The ionic conductivity of the polymer electrolyte with an ABS/PMMA ratio of 6/4 and a plasticizer content of 60% was highest when the LiClO₄ content was 4.8%. The transference numbers (T ₊) of the polymer electrolytes were measured using the steady-state current method, and the T ₊ values were found to be less than 0.5. The electrolyte system was found to have an electrochemical stability window up to 4.5 V. The properties of the electrode interface in contact with the polymer electrolyte were also investigated by impedance spectroscopy, and the evolution of these spectra as a function of storage time was explained and interpreted using a solid-polymer layer (SPL) model. The time evolution of the impedance parameters indicated that a passivation film grew rapidly on the lithium surface immediately after assembly of the cell. Electronic Publication     

Use of FT-IR Spectrometry for On-Line Detection in Temperature Rising Elution Fractionation

Summary: Temperature rising elution fractionation (TREF) has become a popular analytical technique that is able to determine the chemical composition distribution (CCD) of an ethylene/α-olefin copolymer. An infrared (IR) detector is commonly used in TREF detection to measure the concentration of the polymer solution exiting the column as a function of elution temperature. The chemical composition of the eluting polymer at a given elution temperature can be predicted from the relationship between comonomer content and TREF elution temperature pre-established through ¹³C nuclear magnetic resonance (NMR) analysis of TREF fractions. In this article, a Fourier transform infrared (FT-IR) spectrometer has been coupled with a TREF instrument to provide a more powerful tool for characterizing complex olefin copolymers. The Partial Least Squares (PLS) technique is used when analyzing the FT-IR spectra of the eluting polymer solutions. The power of on-line FT-IR detection in TREF is demonstrated using a few complex copolymer systems, such as ethylene-octene copolymer, polystyrene grafted ethylene-vinyl acetate copolymer and ethylene-methyl acrylate copolymer.     

Miscibility of poly(vinyl methyl ether) and poly(styrene-co-2-vinylnaphthalene) blends by FT-IR spectroscopy and Tg measurements

Miscibility of blends consisting of poly(vinyl methyl ether) (PVME) and poly(styreneco-2-vinylnaphthalene) [P(S-co-2VN)] was investigated by means of Fourier transform infrared (FT-IR) spectroscopy and thermal analysis. Copolymers containing 21, 51, and 84 wt % of styrene were synthesized by radical polymerization. Based on optical clarity and glass transition temperatures, it was shown that the miscibility in P(S-co-2VN)/PVME blends is largely affected by compositions of the copolymers as well as concentrations of the blend. From the FT-IR results, the relative intensity at 1100 cm^?1 peak of COCH₃ band of PVME and the position of naphthyl ring of 2VN were sensitive to the miscibility of the blends. It was observed that blends of PVME with P(S-co-2VN) of 84 wt % styrene or P(S-co-2VN) of 51 wt % styrene are miscible over the entire concentration ranges of the blends. Blends of PVME with P(S-co-2VN) containing 21 wt % of styrene are immiscible below 65 wt % PVME. In the miscible P(S-co-2VN)/PVME blends, there was observed a large shift in the naphthyl frequency at a characteristic wavelength of 748 cm^?1. © 1993 John Wiley & Sons, Inc.     

Effect of PEG on the crystallization of PPDO/PEG blends

A new biodegradable polymer system, poly(p-dioxanone) (PPDO)/poly(ethylene glycol) (PEG) blend was prepared by a solvent casting method using chloroform as a co-solvent. The PPDO/PEG blends have different weight ratios of 95/5, 90/10, 80/20 and 70/30. Crystallization of homopolymers and blends were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). When 5% of PEG was blended, the crystallization exothermal peaks (T_c) of PPDO increased sharply and the crystallization exothermal peaks (T_c) of PEG decreased slightly compared with the homopolymers. The crystallization rates of both components increased, and caused greater relative crystallization degree (X_t%). But when the content of PEG was more than 5%, the crystalline behaviors of blends had no more significant changes accordingly. The melting points of each sample varied little over the entire composition range in this study. The nonisothermal crystallization of PPDO homopolymer and blend (PPDO/PEG = 70/30) were also studied by DSC. The crystallization began at a higher temperature when the cooling rates were slower. The nonisothermal crystallization kinetics of blends was analyzed by Ozawa equation. The results showed that the Ozawa equation failed to describe the whole crystallization of the blend, but Mo equation could depict the nonisothermal crystallization perfectly.     

UV-curable epoxy systems containing hyperbranched polymers: Kinetics investigation by photo-DSC and real-time FT-IR experiments

The effect of the presence of a hyperbranched OH-functionalized polymer (HBP) on the kinetics of cationic photopolymerization of an epoxy system was investigated employing two complementary techniques, photo-DSC and real-time FT-IR spectroscopy.Lower rates of cross-linking reactions and higher conversion degrees were obtained in photo-DSC experiments with respect to real-time FT-IR spectroscopy. A limited amount (10% wt) of HBP influenced to a certain extent the cure kinetics of the epoxy resin followed by RT-IR; a final conversion of epoxy groups equal to 100% was achieved by increasing the content up to 20% wt The addition of 10% wt of HBP leaves the cure kinetics of the CE resin studied by p-DSC almost unchanged. By increasing the HBP content, a slightly lower reaction rate is observed at lower reaction times. The presence of the HBP produced a continuous decrease of the T_g of the UV-cured epoxy resin but only modest reductions in its thermo-oxidative stability.     

Chromatic changes in the blends of electroactive polymers with comb-shaped flexible polymers

The effect of blending of alkylated polymers, which have different backbone structures, was investigated in order to improve the electronic properties of conducting polymers. Comb-shaped flexible polymer, poly(octadecyl acrylate) (PODA), was blended with rigid alkylated conducting polymers, poly(3-dodecyl-thiophene)(PDDT), and polyaniline emeraldine base (PANI)/p-dodecyl-benzenesulfonic acid (DBSA) complex, respectively, to investigate the effect of long alkyl chain of flexible polymer on the conformational mode change of rigid backbones and the effect of intermolecular interaction between these alkylated polymers. Optical microscopy was applied to observe the morphology change and obtain the phase diagrams of these blends. The intermolecular interactions that occurred in these blends were explained for each different characteristic peak obtained with FT-IR spectra. Solvatochromism (red-shift) of PDDT/PODA binary blends in solid state due to the planarity change of rigid backbone in the presence of PODA and electrochromism of PANI(DBSA)₄/PODA ternary blends due to the hydrogen bonding between the nitrogen cation of PANI complex and carbonyl group of PODA are observed in UV-Vis-NIR spectra. Interestingly, the increase of conductivity was observed in the presence of 5 wt% of PODA in PDDT/PODA binary blends and a homogeneous smectic liquid crystalline structure was clearly confirmed by cross polarized optical microscopy in PANI(DBSA)₄/PODA ternary blends.     

Thermodynamic study of poly(vinyl chloride)/polyester blends by inverse-phase gas chromatography at 120°C

Polymer/polymer interaction parameters χ′₂₃ have been measured at 120°C as a function of polymer concentration for six different poly(vinyl chloride)/linear aliphatic polyester blends. The technique used is inverse-phase gas chromatography with several molecular probes. The polymers investigated are poly(DL-lactide), poly(ethylene succinate), poly(ethylene adipate), poly(butylene adipate), poly(δ-valerolactone), poly(ε-caprolactone) and poly(hexamethylene sebacate). Probe/polymer interaction parameters χ₁₂ and polymer/polymer interaction parameters χ′₂₃ values are dependent upon the methylene to carbonyl ratio of the polyester, reaching a minimum for a value of 5, this ratio corresponding to poly(ε-caprolactone) blends. Results are interpreted in terms of pairwise interactions between carbonyl, methylene, and [CHCl] groups.     

Fluorination of poly(p-phenylene) using TbF4 as fluorinating agent

The fluorination using TbF₄ as fluorinating agent was successfully performed on poly(p-phenylene). The method allows the fluorine content of the polymer to be controlled and the formation of structural defects, such as dangling bonds, to be significantly decreased by comparison with the direct fluorination using pure F₂ gas. The aromatic character of the phenyl ring is partly maintained through the fluorination contrary to the direct fluorination (using pure F₂ gas), for which a quasi-perfluorination and a partial decomposition of the polymer occur. Complementary analytical techniques have been used, such as ¹⁹F and ¹³C solid state NMR, FT-IR and EPR to compare the samples as a function of the reaction conditions.     

Isothermal crystallization kinetics of AB2 hyper-branched polymer (HBP)-filled polypropylene (PP)

In this paper, the isothermal crystallization kinetics of pure polypropylene (PP) and AB₂ hyper-branched polymer (HBP)/PP blends have been investigated by differential scanning calorimetry (DSC). During isothermal crystallization, the crystallization rates of the blends are higher than those of PP. Furthermore, in the blends with different HBP contents, the value of t _1/2 became smaller with increasing HBP content; however, the crystallization rate of the blend decreased slightly when the content of HBP is 5 %. An increase in the Avrami exponent means the addition of HBP influences the mechanism of nucleation and the growth of PP crystallites. In addition, the crystallization activation energy of pure PP and HBP/PP blends were also discussed, and the result showed that the crystallization activation energy has decreased remarkably in HBP/PP blends.     

Isomorphic behavior of poly(aryl ether ketone) blends

Blends of various poly(aryl ether ketones) have been found to exhibit a range of miscibility and isomorphic behavior. This range is dependent on molecular weight; however, for poly(aryl ether ketones) with number-average molecular weight of 20,000, this range is about ±25% difference in ketone content. All miscible blends exhibit isomorphism, and all immiscible blends exhibit no evidence of isomorphism. The dependence of the glass transition temperature T_g versus composition exhibits a minimum deviation from linearity whereas the melting temperature T_m versus composition exhibits a pronounced maximum deviation from linear behavior. The crystalline melting point versus composition for isomorphic blends is considerably different than for random copolymers with isomorphic units. Homopolymers and random copolymers exhibit a melting point that is a linear function of ketone content (increasing ketone content increases T_m). For blends, the melting point is essentially the same as that of the higher melting constituent until high levels of the lower melting constituent are present. The observed melting point versus composition behavior will be interpreted using classical theory to calculate the components of the liquid and crystalline phase compositions. As a miscible blend is cooled from the melt, essentially pure component of the highest melting point crystallizes out of solution, as predicted by calculated solid-liquid phase diagrams. This occurs until the crystallization is complete owing to spherulitic impingement. At high concentrations of the lower melting constituent, lower melting points will be observed because the highest melting constituent will be depleted before the crystallization is complete. In many miscible blends involving addition of an amorphous polymer to a crystalline polymer, the degree of crystallinity of the crystalline polymer has been shown to increase. On the basis of evidence presented here, it is hypothesized that dilution by a miscible, amorphous polymer allows for a higher level of crystallinity.     

PVT and oscillatory tests to analyze pressure effects on polypropylene/Rodrun LC3000 blends: Determination of the pressure dependency of the viscosity

A combined analysis of Pressure-Volume-Temperature (PVT), Dynamic Mechanical Thermal Analysis (DMTA) and oscillatory flow measurements for blends of a polypropylene (PP) with a commercial liquid crystalline polymer (Rodrun LC3000) is presented. This analysis allows the determination of the pressure-viscosity coefficient b = ∂lnη₀/∂P. This coefficient depends on the Rodrun LC3000 content, increasing with it and is of the same order of magnitude as values reported for several commercial polymers showing a similar dependence of the viscosity on pressure. The analysis of the pressure dependence of Tg (related to b) leads to the conclusion that the number of segments involved in the glass transition of PP increases with the Rodrun LC3000 content, thus demonstrating that the polymers are not totally immiscible. As far as the authors know, this is the first time that the dependence of the viscosity on the pressure has been reported for thermoplastic/liquid crystalline polymer blends.     

Melting behavior,miscibility, and hydrogen-bonded interactions of poly(ε-caprolactone)/poly(4-hydroxystyrene-co-methoxystyrene) blends

The miscibility of poly(4-hydroxystyrene-co-methoxystyrene) (HSMS) and poly(ε-caprolactone) (PCL) was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). HSMS/PCL blends were found to be miscible in the whole composition range by detecting only a glass transition temperature (T_g), for each composition, which could be closely described by the Fox rule. The crystallinity of PCL in the blends was dependent on the T_g of the amorphous phase. The greater the HSMS content in the blends, the lower the crystallinity. The polymer–polymer interaction parameter, χ₃₂, was calculated from melting point depression of PCL using the Nishi-Wang equation. The negative value of χ₃₂ obtained for HSMS/PCL blends has been compared with the value of χ₃₂ for poly(4-hydroxystyrene) (P4HS)/PCL blends. The specific nature, quantitative analysis, and average strength of the intermolecular interactions in HSMS/PCL and P4HS/PCL blends have been determined at room temperature and in the molten state by means of Fourier transform infrared spectroscopy (FTIR) measurements. The FTIR results have been in good correlation with the thermal behavior of the blends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 95–104, 1998     

Miscibility and orientation behavior of poly(vinyl alcohol) / poly(vinyl pyrrolidone) blends

The miscibility of poly(viny1 alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) blends is investigated by differential scanning calorimetry (DSC) and wide-angle x-ray diffraction (WAXD). The molecular orientation induced by uniaxial stretching of the blends is also examined by WAXD and birefringence measurements. It is shown by the DSC thermal analysis that the polymer pair is miscible, since a single glass transition temperature (T_g) is situated between the T_gs of the two homopolymers at every composition. The T_g versus composition curve does not follow a monotonic function but exhibits a cusp point at a PVP volume fraction of a little under 0.7, as in a case predicted by Kovacs' theory. The presence of a specific intermolecular interaction between the two polymers is suggested by an observed systematic depression in the melting point of the PVA component. A negative value of the polymer-polymer interaction parameter, χ₁₂ = 0.35 (at 513 K), is estimated from a thermodynamic approach via a control experiment using samples crystallized isothermally at various temperatures. The extent of optical birefringence (Δn) of the drawn blends decreases drastically with increasing PVP content up to 80 wt %, when compared at a given draw ratio, and ultimately Δn is found to change from positive to negative at a critical PVP concentration of a little over 80 wt %. Discussion of the molecular orientation behavior takes into consideration a birefringence compensation effect in the miscible amorphous phase due to positive and negative contributions of oriented PVA and PVP, respectively.