Plasticizer migration from plasticized into unplasticized poly(vinyl chloride)

There exist important industrial applications, such as hoses or plastic windows, dealing with closely combining plasticized and rigid poly(vinyl chloride). Nevertheless, migration of plasticizer causes severe variation of the mechanical performance of the end-products. This work comprises an effort to investigate and understand these phenomena, also as an extension of previous work of ours in migration to liquid environments. The common system plasticized PVC/dioctylphthalate/unplasticized PVC was studied under two-sided diffusion conditions, i.e., from a thin sheet of plasticized sheet. The whole assembly was placed between two glass plates and then was held in an oven at 64°C to simulate accelerated test conditions. Some pressure was also applied to ensure perfect contact between the plastic sheets. Three different levels of initial plasticizer concentration (48, 66, and 100 phr) have been considered for a period of about five months, until equilibrium was reached. During this period the migration process was monitored by weight changes. Plots of M_t/M_∞ vs. t^½, where M_∞ the amount migrated at equilibrium and M_t the amount lost at time t, resulted in evident linear relationship. Therefore, it was proved that the Fick's law approximation for short times can be used to describe the migration kinetics for this solid/solid system. On the other hand, macroscopic observations revealed that no plasticizer was accumulated at the interface, i.e. all plasticizer leaving the plasticized sheet entered the rigid ones. Finally, it seems that the controlling stage is the diffusion inside plasticized PVC while possible annealing of the plasticized polymer structure cannot be excluded.     

Effect of ketal group in castor oil acid-based plasticizer on the properties of poly(vinyl chloride)

Two castor oil acid esters containing a ketal or ketone group (KCL or CL), as alternative plasticizers for poly(vinyl chloride) (PVC), were prepared. The structures were confirmed by ¹H NMR and FTIR spectroscopies. The effects of the presence of a ketal or ketone group in these compounds on PVC plasticization were examined. The DMA and SEM results showed that both plasticizers were miscible with PVC and exhibited excellent plasticizing properties, compared to those of dioctyl phthalate (DOP). The PVC plasticized by KCL displayed a lower T_g value of 20.6 ° C, which was lower than that of PVC plasticized with DOP (22.3 ° C) and PVC plasticized with CL (40.5 ° C). Tensile tests indicated that PVC plasticized using KCL showed a 37% higher of elongation at break than PVC plasticized by CL and 30% higher than PVC plasticized by DOP. The plasticizing mechanism was also investigated. Moreover, exudation, volatility, and extraction tests, along with TGA indicated that the presence of ketal groups effectively improved the migration resistance of plasticizer and the thermal stability of PVC blends. Taken together, introducing ketal groups into plasticizer might be an effective strategy for improving its plasticizing efficiency.     

Properties of poly(vinyl chloride) incorporated with a novel soybean oil based secondary plasticizer containing a flame retardant group

A novel bio‐based plasticizer containing flame retardant groups based on soybean oil (SOPE) was synthesized from epoxidized soybean oil (ESO) and diethyl phosphate through a ring‐opening reaction. PVC blends plasticized with ESO and SOPE were prepared, respectively. Properties including rheological behavior, thermal stability, flame retardant performance, mechanical properties of PVC plasticized with ESO and SOPE were carefully studied. The results showed that the plasticized PVC blends indicated better compatibility, thermal, and mechanical properties. As a novel bio‐based plasticizer containing flame retardant groups, the TGA data indicated that the thermal degradation temperature of PVC blends plasticized with SOPE could reach to 275.5°C. LOI tests and SEM indicated that the LOI value of PVC blends could increase from 24.2 to 33.6%, the flame retardant performance of SOPE was put into effect by promoting polymer carbonization and forming a consolidated and thick flame retardant coating quickly, which is effective to prohibit the heat flux and air incursion. The enhancement in flame retardancy will expand the application range of PVC materials plasticized with SOPE. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42111.     

Polyethylene glycol grafting and attachment of encapsulated magnetic iron oxide silica nanoparticles onto chlorosilanized single-wall carbon nanotubes

It is demonstrated that functionalization of single-wall carbon nanotubes (SWCNTs) can be carried out using simple chlorosilane chemistry, which allows coupling of the SWCNTs with external chemical species. As a result, organic polymers and magnetically iron oxide-in-silica nanoparticles are specifically bonded onto SWCNTs. It is also found that the SWCNTs functionalized with long PEG chains greatly enhance dispersion of the carbon structure in water. Furthermore, the SWCNT-COO-Si(Fe₃O₄@SiO₂) can be quickly separated and redispersed from their aqueous colloid with the application of external magnetic field.     

Evaluation of PP/EPDM nanocomposites filled with SiO2, TiO2 and ZnO nanofillers as thermoplastic elastomeric insulators

Abstract

Thermoplastic elastomer, which has important characteristics for cable insulation, was developed by melt blending of polypropylene (PP) with ethylene propylene diene monomer (EPDM) at various blend ratios together with SiO₂, TiO₂ and ZnO nanofillers at fixed loading of 2 vol.-%. The influence of EPDM content and the presence of nanofillers in the blend on burning rate, hydrophobicity and dielectric breakdown strength were investigated. Burning rate of PP/EPDM/ZnO was significantly reduced, implying that there was an improvement in fire retardancy with the addition of ZnO nanofillers in the polymer blend. Both SiO₂ and ZnO filled system showed an improvement in hydrophobicity. Furthermore, dielectric breakdown strength showed higher value in EPDM rich blends. In addition, the presence of nanofillers deteriorated the dielectric breakdown strength of PP/EPDM nanocomposites.     

A strategy to prepare internally plasticized PVC using a castor oil based derivative

Internally plasticized PVC was prepared via chemical reaction of azide PVC and alkynyl group containing castor oil methyl ester. The chemical structure of alkynyl group containing castor oil methyl ester and internally plasticized PVC was characterized with FT-IR and ¹H NMR. Properties of internally plasticized PVC, including thermal stability, tensile tests and resistance to extraction in different solvents, was investigated. The results showed that alkynyl group containing castor oil methyl ester, as internal plasticizer of PVC, not only decreased the T_g of PVC from 84.6 °C to 41.6 °C efficiently, but also presented no plasticizer loss in five different solvents. The tensile tests showed that elongation at break and tensile strength of internally plasticized PVC was 353.8% and 18.1MPa. The internally plasticized PVC has potential application in replacing the traditional PVC material in PVC products with high durability.     

Electrochemical characterization and reactivity of Pt nanoparticles supported on single-walled carbon nanotubes

Carbon nanotubes have been proposed as advanced metal catalyst support for electrocatalysis. In this paper, Pt nanoparticles supported on single-walled carbon nanotubes (SWCNTs)-Pt, were prepared using a solid-state reaction between the SWCNTs and two different Pt precursors, bis(dibenzylideneacetone)platinum [Pt(DBA)₂] or tri(dibenzylideneacetone)platinum [Pt(DBA)₃]. TEM images of the samples show Pt nanoparticles with a particle size around 2.5 nm with a high degree of dispersion on the SWCNTs. A detailed electrochemical characterization of the surface of the samples including irreversibly adsorbed adatoms of Bi and Ge as probe reactions has been carried out. It has been stated that SWCNTs-Pt samples subjected to the classical electrochemical activation induce a serious sintering of the Pt nanoparticles.     

Synthesis of TiO2/PAA nanocomposite by RAFT polymerization

Due to the strong tendency of nanoparticles such as metal oxides to agglomerate, homogeneous dispersion of these materials in a polymeric matrix is extremely challenging. In order to overcome this problem and to enhance the filler-polymer interaction, this study focused on living polymerization that was initialized from the surface of titania nanofillers. A new method for synthesizing TiO₂/polymer nanocomposites was found with a good dispersion of the nanofillers by using the bifunctional RAFT agent, 2-{[(butylsulfanyl)carbonothioyl]sulfanyl}propanoic acid). This RAFT agent has an available carboxyl group to anchor onto TiO₂ nanoparticles, and an SC(SC₄H₉) moiety for subsequent RAFT polymerization of acrylic acid (AA) to form n-TiO₂/PAA nanocomposites. The functionalization of n-TiO₂ was determined by FTIR and partitioning studies, the livingness of the polymerization was verified using GPC and NMR, while the dispersion of the inorganic filler in the polymer was studied using electron microscopy, FTIR and thermal analysis.     

Role of non-functionalized oxide nanoparticles on mechanical properties and toughening mechanisms of epoxy nanocomposites

Over the past few decades, the use of epoxy resins has gained significant attention from worldwide researchers due to its advantages in structural applications in various sectors like automotive, construction, and aerospace industries. This article summarizes and reviews the research on mechanical properties and toughening mechanism of epoxy composites filled with non-functionalized oxide nanoparticles. The incorporation of nanomaterials into the polymer matrix has been considered to be the most effective route to improve the mechanical properties of polymer composites. But the inherent brittle nature and cross-linking ability of epoxy makes it vulnerable to crack initiation and crack growth and limits its use in advanced structural applications. Recently, various kinds of nanofillers such as carbon nanotubes (CNTs), organic and inorganic oxide nanoparticles have attracted industrial interest due to their excellent mechanical, thermal, and electrical properties which can provide a dramatic improvement in the properties of epoxy composites but their dispersion issue, agglomeration and bundling problems deteriorate several important mechanical parameters of the epoxy composites. To date, no review article focused on the role of non-functionalized oxide nanoparticles on the improvement in mechanical properties of the reinforced epoxy composites. This review article assesses and summarizes some most recent findings on the de-agglomeration process, mechanical properties, and toughening mechanisms of epoxy nanocomposites reinforced with four types of most preferred non-functionalized oxide nanoparticles such as Al₂O₃, TiO₂, SiO_2, and ZrO₂.     

Modified silica to strengthening and toughening soft polyvinyl chloride

Modifying nanoparticles for polymer nanocomposites is important for multifunctional and low-cost developmental direction. However, nanoparticles have several deficiencies, such as dispersion, agglomeration, and poor binding ability with most polymers. This work used soft polyvinyl chloride (PVC with 33.1% plasticizer volume) as the matrix. Polycaprolactone (PCL) was synthesized on the surface of SiO₂ by the bridging effect of silane coupling agent (SiO₂-PCL), which was expected to improve the bond strength between SiO₂ and soft PVC matrix. Moreover, it enhanced the dispersion of SiO₂ in the PVC matrix. The results revealed that SiO₂-PCL was nanodispersed in a soft PVC matrix and played a plasticizer role in the composite, which enhanced the tensile strength and elongation at break of PVC composites. The thermal stability and solvent extraction stability of PVC composites elevated with the increase of SiO₂-PCL content. When the content of SiO₂-PCL was 8 wt%, the tensile strength (14.54 MPa) and elongation at break (149.47%) of PVC composites were the highest, 64.36% and 60.48% higher than those of unfilled PVC, respectively. It was indicated that PVC composites were dramatically toughened and strengthened by modified SiO₂, improving their overall performance.     

Poly(vinyl chloride)/single wall carbon nanotubes composites: Investigation of mechanical and thermal characteristics

Composites of polyvinylchloride (PVC) with single wall carbon nanotubes (SWCNTs) were prepared by plastisol curing. Scanning electron microscopy (SEM) observations revealed that appropriate dispersion of the nanotubes was achieved. The mechanical properties showed that SWCNT improved the Young's modulus and tensile strength of the PVC. The composites have higher elongation at break and toughness as well. By comparing the mechanical properties of the composites, it is found that there is a critical SWCNT loading (about 1 wt%) below which the tensile properties increase with increasing nanofiller concentration. For the composites containing 0.25–0.75 wt% of SWCNT, this situation was observed, whereas for a sample with 1 wt% SWCNT, the mechanical properties decreased due to the agglomeration of the nanotubes. Thermogravimetric analysis indicated that the SWCNT increased T_5%, T_10%, T_50%, T_onset, and T_max and decreased weight loss in the degradation process of the PVC. In addition, by adding SWCNT to the polymer, residual mass at 600°C increased significantly. These results are advantages for the applications of the polymer in which high mechanical properties, including high tensile modulus and toughness, and good thermal properties are needed. J. VINYL ADDIT. TECHNOL., 22:128–133, 2016. © 2014 Society of Plastics Engineers     

Synthesis and properties of sulfonated biphenyl poly(ether sulfone) and its mixed‐matrix membranes containing carbon nanotubes for gas separation

We prepared mixed‐matrix membranes (MMMs) composed of carboxylated single‐walled carbon nanotubes (f‐SWCNTs) and a sulfonated biphenyl poly(ether sulfone) (S‐PPSU) polymer matrix. The thermal stability and properties of the pores of the S‐PPSU and f‐SWCNTs were characterized by thermogravimetric analysis and sorption isotherm curves, respectively; these showed that the surface and pore diameter decreased after the introduction of carboxyl groups to the single‐walled carbon nanotubes (SWCNTs), and the pore properties did not restore original values even when the f‐SWCNTs were preheated to 350 °C to remove carboxyl groups. The gas‐separation measurement showed that the MMMs comprised of the S‐PPSU and f‐SWCNTs possessed better gas‐separation properties than the ones composed of biphenyl poly(ether sulfone) and SWCNTs. The permeability for N₂, O₂, He, and CO₂ and the selectivity for O₂/N₂ and O₂/CO₂ were enhanced simultaneously because of the good dispersion of f‐SWCNTs and the improved interaction between the two phases. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44995.     

New strategy for preparation of LLDPE nanocomposites through tandem catalytic system

Tandem catalytic system composed of the ethylene trimerization catalyst CrCl₃/bis(2-butylsulfanyl-ethyl)amine) (SNS) ( I ) and the ethylene copolymerization catalyst zirconocene dichloride ( II ) has been introduced for preparation of linear low-density polyethylene (LLDPE). The catalytic behavior of the novel catalyst ( I ) activated by modified methyl aluminoxane was tested that afforded 1-hexene (1-C₆) with the activity of 141,370 g 1-C₆/mol-Cr h. The butyl branches in the polymers prepared by tandem catalysis method were determined utilizing Fourier transform infrared (FTIR) spectroscopy for the first time. The higher Cr/Zr molar ratio led to increasing the butyl content within the prepared copolymer up to 10.38 butyl branches per 1000 C in the polymer chain. LLDPE nanocomposites having different types of nanofillers (TiO₂, Santa Barbara Amorphous-15, and Fe₃O₄ magnetic nanoparticles) were prepared and analyzed by FTIR, scanning electron microscopy (SEM), differential scanning calorimetry, and thermogravimetric analysis. Increasing the sonication time up to 60 min enhanced the nanoparticles dispersion in the polymeric matrix. SEM images of the nanocomposites with various amounts of nanofillers, showed the best dispersion of the nanofillers in the presence of 50 mg nanofiller in toluene solvent. The presence of the nanofillers also increased the hydrophilicity of the polymer surface. Antibacterial activity against Gram-negative bacteria was also observed for the prepared nanocomposites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47497.     

Evaluation effects of biobased plasticizer on the thermal,mechanical, dynamical mechanical properties,and permanence of plasticized PVC

Sunflower oil (SO) is a renewable resource that can be epoxidized, and the epoxidized SO has potential uses as an environmentally friendly in polymeric formulations, especially for poly (vinyl chloride) (PVC). Epoxidized sunflower oil (ESO) was prepared by treating the oil with peracetic acid generated in situ by reacting glacial acetic acid with hydrogen peroxide. Epoxidation was confirmed using spectroscopic and titration methods. ESO was used as a coplasticizer in PVC for the partial replacement of di‐(2‐ethyl hexyl) phthalate (DEHP). The effect of ESO on the thermal stability of plasticized PVC was evaluated by using synmero scale for the sheets. In presence of ESO plasticized PVC samples showed a reduction in discoloration and the number of conjugated double bonds. By using thermogravimetry, the incorporation of 15/45 of ESO/DEHP in PVC presents the lowest weight loss. The results of the shore hardness and mechanical properties showed that a proportion of DEHP could be substituted by ESO. By use of DMA, the formulation which contains 25 % wt of ESO in plasticizer system shifts the glass transition temperature (T_g) to ambient temperature. The migration phenomenon was studied on PVC based samples plasticized with DEHP and ESO in varying amounts. The migration was monitored by the weight loss percentage of the samples immersed into n‐hexane or heated in an oven. The amount of extracted or volatilized DEHP is proportional to the added ratio of ESO in plasticizer system. All of this favored the partial replacement of DEHP by ESO as biobased plasticizer for flexible PVC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on ionic liquid [bmim]PF<Subscript>6</Subscript> and [hmim]PF<Subscript>6</Subscript> as plasticizer for PVC paste resin

Two kinds of room temperature ionic liquids, [bmim]PF₆ (1-butyl-3-methylimidazolium hexafluorophosphate) and [hmim]PF₆ (1-hexyl-3-methylimidazolium hexafluorophosphate), were respectively used as plasticizer for PVC paste resin. The mechanical properties, thermal and ultraviolet ray stabilities, and migration characteristics of the PVC paste resin samples were determined by universal testing machine, TG/DTA, and HPLC. The results showed that the tensile strength and elastic modulus decreased, the elongation at break and thermal stability of PVC paste resin membranes were improved with the increasing of [bmim]PF₆ or [hmim]PF₆ dosages. The immersed time and temperature could accelerate leaching and migration of plasticizers in plasticized PVC paste resin films. Moreover, the effect of solvent environment on migration amount was also studied.     

Synthesis and Characterization of Anti-fungus,Anti-corrosion and Self-cleaning Hybrid Nanocomposite Coatings Based on Sol–Gel Process

Anti-corrosion, anti-fungus, and self-cleaning properties of coatings containing ZnO–TiO₂, SiO₂–TiO₂ and SiO₂/TiO₂/ZnO nanoparticles synthesized based on sol–gel precursors using tetra methoxysilane, 3-glycidoxypropyl trimethoxysilane, tetra (n-butyl orthotitanate) and zinc acetate dihydrate were investigated by FESEM, EDAX and TEM analyses. Results indicated uniform dispersion of inorganic nanoparticles in the range of 20–40 nm in size. Anti-corrosion property of the hybrid coating was characterized by EIS measurements and parametrically analyzed in an equivalent circuit when the coating was exposed to salt solution. Results showed that, ZnO and TiO₂ nanoparticles enhance anti-corrosion property of the hybrid coatings. Anti-fungus and anti-bacterial properties of the coatings were determined by diameter of inhibition zone and inhabitation of bacterial growth, respectively. The coating containing ZnO and TiO₂ nanoparticles showed anti-fungus and anti-bacterial properties which were related to their photocatalytic properties. Degradation of methylene blue in aqueous solution was determined by UV–Visible tests which indicated self-cleaning property of the coatings containing ZnO and TiO₂ nanoparticles.     

Preparation of TiO2/carbon nanotubes photocatalysts: The influence of the method of oxidation of the carbon nanotubes on the photocatalytic activity of the nanocomposites

A method for the preparation of efficient TiO₂/multi-wall carbon nanotubes nanocomposite photocatalysts by precipitation of anatase TiO₂ nanoparticles onto differently oxidized carbon nanotubes is presented. The precursor compound titanium(IV) bromide was hydrolyzed producing pure anatase phase TiO₂ nanoparticles decorated on the surface of the oxidized carbon nanotubes. The oxidative treatment of the carbon nanotubes influenced the type, quantity and distribution of oxygen-containing functional groups, which had a significant influence on the electron transfer properties, i.e., the photocatalytic activity of the synthesized nanocomposites. The results of C.I. Reactive Orange 16 photodegradation in the presence of all the synthesized nanocomposites showed their better photocatalytic activity in comparison to the commercial photocatalyst Degussa P-25.     

Plasticizer diffusion into PVC particles as studied by ESR spin probe method

Summary The spin probe technique of electron spin resonance (ESR) spectroscopy has been applied for studying the plasticizer diffusion, migration, and redistribution processes in suspension polymerized PVC particles. In the first series of experiments six PVC powder samples with different K values (58, 61, 64, 67, 70, and 72) were mixed with diisooctyl phthalate (DOP) containing 10^–4 M 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) as stable free radical spin probe. In the second run TEMPO-doped dry PVC powders were mixed with DOP plasticizer. Finally we studied the plasticizer transport phenomena between plasticized and non-plasticized polymer particles in powder mixtures. The observed diffusion properties of different samples were interpreted in terms of the different porosities of powders.     

Photocatalytic degradation of flexible PVC/TiO2 nanohybrid as an eco-friendly alternative to the current waste landfill and dioxin-emitting incineration of post-use PVC

Photo-degradable poly(vinyl chloride) (PVC)/titanium dioxide (TiO₂) nanohybrid has been investigated to be utilized as an eco-friendly alternative strategy to the current waste landfill and toxic byproduct-emitting incineration of PVC wastes. Thus, the present study suggests a novel idea related to preparing the photocatalytically degradable nanohybrid through TiO₂ nanoparticle-integrated hyperbranched poly(ε-caprolactone) (HPCL-TiO₂). The main aim of this study is to find a solution to the unresolved problem in the conventional PVC/TiO₂ composites related to the poor dispersion of the nanoparticles in PVC polymer. First, TiO₂ nanoparticles are prepared by a sol-gel process, and the size of the particle is about 5-10 nm in diameter as measured by using a transmission electron microscopy (TEM) and dynamic light scattering (DLS). The hyperbranched poly(ε-caprolactone) (HPCL) with numerous COOH groups and good miscibility with PVC as a binder for TiO₂ nanoparticles is prepared from moisture-sensitive catalyst-free polymerization of 2,2-bis[ω-hydroxy oligo(ε-caprolactone)methyl]propionic acids followed by modification reaction using pyridinium dichloromate (PDC), then characterized with ¹H NMR and ¹³C NMR analyses. The integration of TiO₂ nanoparticles onto HPCL is carried out by a dip-coating method based on the spontaneous self-assembly between TiO₂ nanoparticles and HPCL, and the loading amount of the nanoparticles in the HPCL-TiO₂ is determined to be ca. 3.3 wt% by X-ray photoelectron spectroscopy (XPS). Then, the HPCL-TiO₂ is blended with PVC by solution blending in THF as solvent, and the resulting dispersibility of TiO₂ nanoparticle in PVC is characterized by field emission scanning electron microscopy (FESEM) equipped with energy dispersive spectrometry (EDS), which exhibits the TiO₂ nanoparticles are well-dispersed in PVC matrix, while some agglomerates are observed in the PVC/TiO₂ sample prepared from TiO₂ nanoparticle itself. The photocatalytic degradation of the samples are examined and verified from the change of surface morphology, chemical structure, molecular weight, and molecular-level structure after UV irradiation through field-emission scanning electron microscopy (FESEM), UV-visible spectroscopy, gel permeation chromatography (GPC), and positron annihilation lifetime spectroscopy (PALS). The remarkable photocatalytic degradation is observed in the PVC/HPCL-TiO₂, and the structural change accompanied by the degradation of the irradiated sample can clearly explained.     

Development of nanocomposites based on organically modified montmorillonite and plasticized PVC with improved barrier properties

Montmorillonite (MMT) was organically modified with tributyl citrate (TBC). Organoclays (OMMTs) were processed with diisononyl phthalate (DINP)‐plasticized polyvinyl chloride (PVC) to form polymer nanocomposites. The produced composite materials showed a contradictory change in properties to that expected of a layered silicate nanocomposite, with a decreased E‐modulus and increased gas permeability compared with a material without OMMT. It was experimentally shown that the TBC modifier was extracted from the OMMT and was dispersed in the PVC/DINP matrix, whereupon the OMMT collapsed and formed micrometer‐sized agglomerates. Further investigation revealed that TBC has a significant effect on the gas permeability and the E‐modulus, even at low additions to a DINP‐plasticized PVC. A PVC nanocomposite with the TBC acting as both the OM for MMT and as the primary plasticizer was produced. This material showed a significantly increased E‐modulus as well as a decrease in gas permeability, confirming that it is possible to develop a nanocomposite based on plasticized PVC, if both the organo‐modification of the MMT and the formulation of the matrix are carefully selected. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42876.