Thermal Degradation Kinetics of Plasticized Poly (Vinyl Chloride) with Six Different Plasticizers

Plasticized PVC formulated with different kinds of normally used plasticizers, including bis(2-ethylhexyl) phthalate (DOP), dioctyl terephthalate (DOTP), acetyl tri-n-butyl citrate (ATBC), acetyl trioctyl citrate (ATOC), trioctyl trimellitate (TOTM), and a new vegetable devived plasticizer, isosorbide ester (ID-37), were prepared by a melt blending method. The effect of plasticizer on the thermal degradation behavior of plasticized PVC was investigated by thermal gravimetric analysis (TGA). The activation energies were calculated by three well known methods, developed by Flynn-Wall-Ozawa (FWO), Friedman and Kissinger, respectively. The TGA conducted in N₂ atmosphere showed that the type of plasticizer had an obvious influence on the thermal stability of plasticized PVC. It was found that the peak temperatures (T_P) of the thermal degradation processes shifted to higher temperature with the increase of the heating rate, with two processes being shown. The activation energy of the first thermal decomposition process (E₁), calculated by the Kissinger method, was between 118 and 130 kJ/mol, while the activation energy of the second thermal decomposition process (E₂) was between 261 and 305 kJ/mol, except 499 kJ/mol for the PVC/TOTM formulation. The corresponding values of E₁ and E₂ obtained by the Flynn-Wall-Ozawa method were similar to the above data. E of the sample with TOTM also showed a higher value than the others; the results demonstrated that the PVC plasticized with TOTM was more thermally stable than with the others. The activation energies for certain conversion degrees were calculated by the Friedman method and the FWO method. The value of activation energy for 20%, 50%, and 80% conversion calculated by the Friedman method, exhibited an apparent difference from that calculated by the Flynn-Wall-Ozawa method; the results showed that the value of E obtained by the Friedman method was much more reasonable than that obtained by the Flynn-Wall-Ozawa method.     

Effect of different plasticizers on the secondary relaxation of poly(vinyl chloride)

Samples of poly(vinyl chloride) plasticized with variable amounts of either dibutyl phthalate (DPB) or dicyclohexyl phthalate (DCHP) were investigated by dynamic-mechanical measurements in the β relaxation temperature range. In this range of temperature, a superposition of the relaxation due to the cyclohexyl group with the PVC β peak was found for the samples plasticized with DCHP. By studying the dependence of the activation energy and of the peak broadness on the DCHP concentration it was possible to show that the PVC β relaxation is reduced to zero at the critical plasticizer weight fraction W₁ = 0.2. For the PVC-DBP series the β peak disappears at the same plasticizer content. These results strengthen the hypothesis that the β peak of PVC is due to a kind of cooperative motion since 1 mole of plasticizer for every 20 repeating units of the polymer is sufficient to suppress the PVC β relaxation.     

Preparation and characterization of a magneto-polymeric nanocomposite: Fe3O4 nanoparticles in a grafted, cross-linked and plasticized poly(vinyl chloride) matrix

In this work two kind of materials: (1) grafted, cross-linked and plasticized poly(vinyl chloride) (PVC) “plastic films” and (2) magnetic plastic films “magneto-polymeric nanocomposites” were prepared. Precursor solutions or “plastisols” used to obtain the plastic films were obtained by mixing PVC (emulsion grade) as polymeric matrix, di(2-ethylhexyl)phthalate (DOP) as plasticizer, a thermal stabilizer based in Ca/Zn salts, and a cross-linking agent, 3-mercaptopropyltrimethoxysilane (MTMS) or 3-aminopropyltriethoxysilane (ATES), at several concentrations. Flexible films were obtained from the plastisols using static casting. The stress–strain behavior and the gel content (determined by Soxhlet extraction with boiling THF) of the flexible films were measured in order to evaluate the effect of the cross-linking agent and their content on the degree of cross-linking. The magneto-polymeric nanocomposites were obtained by mixing the optimum composition of the plastisols (analyzed previously) with magnetite (Fe₃O₄)-based ferrofluid and DOP. Later, flexible films were obtained by static casting of the plastisol/ferrofluid systems. The magnetic films were characterized by the above-mentioned techniques and X-ray diffraction, vibrating sample magnetometry and thermogravimetrical analysis.     

Mechanical spectrum study of glass transition by a composite method

Normalized mechanical spectra of glycerol, 1,2-propanediol carbonate and poly(vinyl chloride)/di(2-ethyl-hexyl) phthalate (PVC/DOP) blends were studied in the temperature range from 100 to 300 K by a composite method. The dynamic glass transition was observed, which exhibits a peak of temperature-dependent loss modulus. The peak moves toward higher temperature with higher measuring frequency, which accords with the relaxation feature of the dynamic glass transition. Another characteristic temperature can be marked in the mechanical spectrum by the onset of storage modulus change, which is labeled as T_gm. T_gm is found to be nearly equal to the calorimetric glass transition temperature in glycerol, 1,2-propanediol carbonate and di(2-ethyl-hexyl) phthalate. As we expected, this onset temperature in the mechanical spectrum has an intimate relation with the calorimetric glass transition of materials, and it can be regarded as a representative when the calorimetric glass transition temperature is not available. Finally, normalized mechanical spectra of PVC/DOP blends with different PVC content were obtained and mechanical glass transition temperatures T_gm were determined.     

Investigations on PMMA-PVdF polymer blend electrolyte with esters of dibenzoic acids as plasticizers

Plasticizers can be used to change the electrical and mechanical properties of polymer electrolytes by reducing the degree of crystallinity and lowering the glass transition temperature. The transport properties of gel type ionic conducting membranes consisting of poly (methyl methacrylate) (PMMA), poly (vinylidene fluriode) (PVdF), Lithium perchlorate (LiClO₄) and dioctyl phthalate (DOP), dibutyl phthalate (DBP), dimethyl phthalate (DMP) or diethyl phthalate (DEP) were studied. The polymer films were characterized by X-ray diffraction, Thermal, Fourier transform infrared and impedance spectroscopic studies. It is found that the addition of DMP as the plasticizer in the PMMA / PVdF-LiClO₄ polymer complex favours an enhancement in ionic conductivity. The temperature dependence of the conductivity of the polymer films seems to obey the VTF relation. The conductivity values are presented and the results are discussed.     

高效液相色谱法同时测定环境水中5种邻苯二甲酸酯

建立了萃取-高效液相色谱法对环境水样中的5种邻苯二甲酸酯类化合物(PAEs)[邻苯二甲酸二甲酯(DMP),邻苯二甲酸二乙酯(DEP),邻苯二甲酸二丁酯(DBP),邻苯二甲酸二辛酯(DOP),邻苯二甲酸二(2-乙基己基)酯(DEHP)]同时进行定量分析的方法。最佳色谱条件:色谱柱:Agilent-C18(250mm×4.6mm,5μm);流动相:甲醇:水(V/V)=80:20(0—10min)—90:10(10—35min);流速:1.0mL/min;紫外检测器,检测波长:280nm。该方法加标回收率在99.00%—100.43%之间,相对标准偏差小于5%。     

Ionic conductance behaviour of plasticized polymer electrolytes containing different plasticizers

The effect of different plasticizers on the properties of PEO-NH₄F polymer electrolytes has been studied. Aprotic organic solvents like propylene carbonate (PC), ethylene carbonate (EC), γ-butyrolactone (γ-BL), dimethylacetamide (DMA), dimethylformamide (DMF), diethylcarbonate (DEC) and dimethylcarbonate (DMC) having different values of donor number, dielectric constant, viscosity etc. have been used as plasticizers in the present study. The addition of plasticizer has been found to modify the conductivity of polymer electrolytes by increasing the amorphous content as well as by dissociating the ion aggregates present in polymer electrolytes at higher salt concentrations. The conductivity enhancement with different plasticizers has been found to be closely related to the donor number of the plasticizer used rather than its dielectric constant. The increase in conductivity with the addition of plasticizer has further been found to be dependent upon the level of ion association present in the electrolytes. The variation of conductivity as a function of plasticizer concentration and temperature has also been studied and maximum conductivity of ∼ 10⁻³ S /cm at room temperature has been obtained. X-ray diffraction studies show an increase of amorphous content in polymer electrolytes with the addition of plasticizers.     

Effect of plasticizer on electrical conductivity and cell parameters of (PVC+KBrO<Subscript>3</Subscript>) polymer electrolyte system

The effect of a plasticizer dimethyl formamide (DMF) on the properties of a potassium ion conducting electrolyte based on polyvinyl chloride (PVC) complexed with potassium bromate (KBrO₃) prepared using solution-cast technique was investigated. Various experimental techniques, such as electrical conductivity (composition and temperature dependence) and transport number measurements, were used to characterize these polymer electrolyte films. It was found that the addition of plasticizer (DMF) significantly improved the ionic conductivity. Transport number for K⁺ ion ranged from 0.95 to 0.97 depending on the composition and temperature. Electrochemical cells of configuration K/PVC+KBrO₃/(I₂+C+electrolyte) and K/PVC+KBrO₃+plasticizer/(I₂+C+electrolyte) were fabricated. The discharge characteristics of the cells were studied under a constant load of 100 kΩ. The open-circuit voltage, short-circuit current, and discharge time for the plateau region were measured. The PVC+KBrO₃ polymer electrolyte system with added plasticizer showed an increased discharge time with respect to pure PVC+KBrO₃ electrolyte system. The features of complexation of the electrolytes were studied by X-ray diffraction.     

Reports on progress in polymer physics in Japan

The Calm microbalance system for plasticizer absorption in PVC resin has been used to study the different absorption behaviors of two different plasticizer systems [diisodecyl phthalate (DidP) and a mixed system] on resins of various origins [50-gal reactor and the large reactor pilot plant (LRPP)] and polymerization conditions [different killing pressures (conversion) and two different chemical additives]. The results show that these two chemical additives do not affect the plasticizer capacity of resin but do increase the maximum rate of plasticizer absorption. Killing pressure (conversion) affects both capacity and rate of absorption.     

Conductivity study of some polymer electrolytes based on polyacrylonitrile

The present paper deals with the room temperature conductivity study of some polymer electrolytes based on polyacrylonitrile, ammonium tetraflouroborate as dopant, and propylene carbonate (PC) and polyethylene glycols (PEG300 and PEG600) as plasticizers. The additions of plasticizers having different dielectric constant have been found to modify the conductivity of polymer electrolytes. The increase in room temperature conductivity with plasticizer addition has been found to depend upon (1) the amount of salt present and (2) amount of plasticizers added. The polymer electrolytes prepared were characterized by X-ray diffraction, scanning electron micrographs, infrared, thermogravimetric, and AC impedance measurements. The highest room temperature conductivity observed in case of these polymer electrolytes was ∼10–13 s/cm.     

基于密度泛函理论的C_(24)H_(38)O_4分子外场效应研究

各种环境毒物危害着人类的健康,塑化剂更是破坏了食品安全.为研究外电场对塑化剂主要成分之一C_(24)H_(38)O_4(邻苯二甲酸二辛酯,dioctyl phthalate,DOP)的影响,采用密度泛函理论B3LYP方法在6-311G(d,p)基组水平上优化了不同静电场0—0.0125 a.u.(0—6.4278×10~9 V/m)作用下DOP分子的基态几何结构,在此基础上利用同样的方法计算了DOP分子的电偶极矩和分子总能量,最后利用含时密度泛函理论在同一基组下研究了不同外电场对DOP分子紫外-可见(UV-vis)吸收光谱产生的影响,并与实验测得的光谱图进行了比较.结果表明:分子几何构型与电场大小呈现强烈的依赖关系,分子偶极矩随着外电场的增强先减小后增加,而分子总能量随着外电场的增强先增加而后急剧减小;DOP分子激发态的振子强度随着外电场的增强而减小,UV-vis吸收峰显著红移.     

Effect of dibutyl phthalate as plasticizer on high-molecular weight poly(vinyl chloride)–lithium tetraborate-based solid polymer electrolytes

A series of different composition of polymer electrolytes-based on poly(vinyl chloride) (PVC) as host polymer, lithium tetraborate (Li₂B₄O₇) as dopant salt, and dibutyl phthalate (DBP) as plasticizer were prepared by solution casting method. The interaction between the PVC, Li₂B₄O₇, and DBP were studied by Fourier transform infrared. The shifting, broadening, and splitting of transmission peaks were the evidences of complexation. The highest ionic conductivity polymer electrolyte of 2.83 × 10⁻⁶ S/cm was achieved at ambient temperature upon addition of 30 wt.% of DBP. In addition, the temperature-dependent conductivity, frequency-dependent conductivity, dielectric permittivity, and modulus studies were performed. The temperature-dependent conductivity of the polymer electrolytes was found to obey the Arrhenius behavior. The thermal stability of polymer electrolytes was verified by thermogravimetric analysis. The lower in glass transition temperature was proven in differential scanning calorimetry, whereas the higher amorphous region within the polymer matrix was demonstrated in X-ray diffraction.     

塑化剂邻苯二甲酸二辛酯的拉曼光谱计算及分析

近几年,国内有关塑化剂的食品安全事件频发,迫切需求加强对于食品中塑化剂的检测研究工作。邻苯二甲酸二辛酯是塑化剂的一种。理论计算和实验测量了邻苯二甲酸二辛酯的拉曼光谱。利用密度泛函理论DFT(B3LYP)的三参数混合方法对其进行了空间结构优化;然后分别用(Hartree-Fock)HF/3-21G和DFT/3-21G两种算法计算了它的拉曼光谱和红外光谱,给出了光谱强度图。实验测量了分析纯级邻苯二甲酸二辛酯的拉曼光谱,并和理论计算结果进行了对比,显示了很好的一致性,与此同时由于计算方法的不同,从图中可以看出Gaussian计算的HF和DFT算法无论是峰的位置还是相对强度等都均存在差别。还给出了常用塑化剂邻苯二甲酸二辛酯的各个键长、键角等空间结构参数,并对邻苯二甲酸二辛酯分子在400～3 500 cm-1区间的振动谱做了指认。报道了常用塑化剂邻苯二甲酸二辛酯的拉曼光谱研究工作。这些工作将有助于拉曼光谱技术在食品检测领域的研究和应用。     

Highly Sensitive Fluorescence Optode Based on Polymer Inclusion Membranes for Determination of Al(III) Ions

This paper reports the use of a polymer inclusion membranes (PIMs) for direct determination of Al(III) ions in natural water by using a fluorescence based optode. The best composition of the PIMs consisted of 60 wt.% (m/m) poly (vinyl chloride) (PVC) as the base polymer, 20 wt.% (m/m) triton X-100 as an extractant, 20 wt.% (m/m) dioctyl phthalate (DOP) as plasticizer and morin as the reagent, was used in this study. The inclusion of triton X-100 was used for enhancing the sorption of Al(III) ions from liquid phase into the membrane phase, thus increasing the optode fluorescence intensity. The optimized optode was characterized by a linear calibration curve in the range from 7.41?×?10^?7 to 1.00?×?10^?4 molL^?1 of Al(III), with a detection limit of 5.19?×?10^?7 molL^?1. The response of the optode was 4 min and reproducible results were obtained for eight different membranes demonstrated good membrane stability. The optode was applied to the determination of Al(III) in natural water samples. The result obtained is comparable to atomic absorption spectrometry method.     

Ionic transport, thermal, XRD, and phase morphological studies on LiCF3SO3-based PVC–PVdF gel electrolytes

The plasticized polymer electrolyte composed of polyvinylchloride (PVC) and polyvinylidene fluoride (PVdF) as host polymer, the mixture of ethylene carbonate and propylene carbonate as plasticizer, and LiCF₃SO₃ as a salt was studied. The effect of the PVC-to-PVdF blend ratio with the fixed plasticizer and salt content on the ionic conduction was investigated. The electrolyte films reveal a phase-separated morphology due to immiscibility of the PVC with plasticizer. Among the three blend ratios studied, 3:7 PVC–PVdF blend ratio has shown enhanced ionic conductivity of 1.47 × 10⁻⁵ S cm⁻¹ at ambient temperature, i.e., the ionic conductivity decreased with increasing PVC-to-PVdF ratio and increased with increasing temperature. A temperature dependency on ionic conductivity obeys the Arrhenius behavior. The melting endotherms corresponding to vinylidene (VdF) crystalline phases are observed in thermal analysis. Thermal study reveals the different levels of uptake of plasticizer by VdF crystallites. The decrease in amorphousity with increase in PVC in X-ray diffraction studies and larger pore size appearance for higher content of PVC in scanning electron microscopy images support the ionic conductivity variations with increase in blend ratios.     

Interfacial enhancement of flexible PVC-silica composites by silane coupling agents

Enhancement of a flexible poly(vinyl chloride) (PVC)-silica composite interface was studied by the application of γ-aminopropyltrimethoxysilane on silica. Composites containing silica and silanized silica up to 25.6 phr (per hundred resin) and prepared by sol-gel technology were subjected to water and water vapor attacks similar to that in their daily use. Silane application resulted in diminishing liquid water and water vapor sorption by about 24.0% and 11.9%, respectively. Equilibrium weight gain values of the composites having different amounts of silica correlated well with a peak at 3400 cm^-1 in the IR spectra which was attributed to the stretching vibration of the O-H group of water. Liquid water and water vapor diffusivities in composites determined by the evaluation of weight gain against time data were about 0.4 x 10^-13 and 0.4 x 10^-12 m² s^-1, respectively. Inhibition of dioctyl phthalate (DOP) migration from composites by silane application was also determined as 24% using UV measurements. The most impressive merit of silane enhancement was observed as the retention of ultimate tensile strength (UTS) under wet conditions. While the untreated silica composite reduced its UTS by about 21.2%, silanized silica composite reduced its UTS by only about 13.6%, on wetting.     

Drastic change of rheological behaviour of Precipitated Calcium Carbonate (PCC) formulations induced by water sorption onto mineral filler surface

The water sorption properties of Precipitated Calcium Carbonate (PCC) formulations have been studied in relation to the rheological behaviour. Uncoated mineral fillers (median diameter 0.85 μm) have been dispersed in an organic liquid used as plasticizer, a dioctylphthalate (DOP), at a concentration of 25% by weight (volume fraction of about 11%). Water sorption isotherms onto PCC in air and in the organic matrix have been constructed. Measurement of water concentration in the DOP permits a complete evaluation of water exchanges at the inorganic (mineral)/organic (plasticizer) interface. Evolutions of yield stress, storage modulus and loss modulus have been determined as functions of the water activity in the system. A drastic change of rheological properties has been observed for water activities above 0.3.     

Ultrasonic treatment and synthesis of sugar alcohol modified Na+-montmorillonite clay

Na⁺-montmorillonite clay (generally referred to as MMT) is very useful for reinforcing polymeric matrix at very low concentrations (typically, 2–5% wt). These clay particles are typically exfoliated before they can demonstrate the significant gains in heat deflection temperature, modulus, and elongation properties. In the case of hydrophilic biopolymer based matrices, such as carbohydrates and chitosan, exfoliating these nanoclay particles needs greater attention because the exfoliation is typically carried out using hydrophobic oligomers through ion-exchange. This study reports a new method of synthesizing completely hydrophilic MMT-assemblages using hydrophilic plasticizers for biopolymers. We used sugar alcohols (glycerol, xylitol with 3 and 5 hydroxyl groups) and polysaccharide maltodextrin to exfoliate the MMT. Sonication was conducted for MMT nanoclay and plasticizers at different weight ratios. It was confirmed that all plasticizer/modifier led to expansion of MMT gallery spacing (d-spacing) and the change in d-spacing could be related to the molecular structure of the plasticizer. Meanwhile, the extent of exfoliation was maximum with maltodextrin (fully exfoliation with 1:10 and 1:20 ratio of MMT:plasticizer) across all test samples and interestingly, glycerol and xylitol samples quickly established within the MMT galleries and exhibited minimal influence with further increase in relative concentrations.     

Effect of plasticizer and surface topography on the cleanability of plasticized PVC materials

A quantitative radiochemical measuring procedure was used to investigate soil adhesion on laboratory-made polyvinyl chloride (PVC) surfaces. The materials contained different plasticizers and microstructures. Both the quality and amount of plasticizers and the microstructure affected the cleanability of the PVC samples. The surface topography and structures were examined with a contact angle meter, atomic force microscopy (AFM) and a contact profilometer.     

Broad band dielectric behaviour of plasticized PEO-based solid polymer electrolytes

The conductivity and dielectric response of poly(ethylene oxide) (PEO) based plasticized polymer electrolyte systems were studied in the broad frequency range from 5 Hz to 1.8 GHz and in the temperature range from 248 K to 353 K. Propylene carbonate (PC) and ethylene carbonate (EC) were used as conventional plasticizers while poly(perfluorinated ethylene methylene oxide) (M03) was used as a new type of plasticizer. PEO-LiN(CF₃SO₂)₂ plasticized with M03 shows high enough conductivity values to be used as electrolyte in rechargeable lithium polymer batteries. At high frequency a dielectric relaxation is observed for pure PEO as well as for the salt containing systems in the GHz region that is assumed to be due to segmental motion of the polymer chains. In the salt containing systems, this relaxation is shifted to lower frequencies relative to that of pure PEO, this is attributed to transient cross-linking. However, at lower frequencies another dielectric response peak was detected in all samples containing salts. The effect of the plasticizer on this relaxation is complex. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.