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 of poly(vinyl chloride) interfaces using slow positron beams

Elemental and X‐ray fluorescence analyses were performed to determine the chemical compositions of insulator and jacket poly(vinyl chloride) (PVC) samples. In addition, differential scanning calorimetry (DSC) measurement was performed to determine their glass‐transition temperatures (T_g) and melting points. The effect of additives on the two investigated samples, as well as on a pure PVC sample, was studied using Doppler‐broadening energy spectra coupled with the slow positron beam technique. Significant variation in the S parameter as a function of positron implantation energy and depth from the surface to the bulk was observed in all samples. The S parameter increased at a very low positron energy (< 1 keV), saturated to about 6 keV, and then decreased up to 27 keV. The S parameter (ΔS) changed to the extent of the change in the breadth of the distribution of free‐volume defects, which was larger in the jacket PVC sample, which had more additives, than in the insulator PVC sample. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3789–3793, 2006     

Self‐crosslinking and cocrosslinking with nitrile rubber of poly(vinyl chloride) with pendent N,N‐diethyldithiocarbamate group

In order to realize the self‐crosslinking and cocrosslinking of poly(vinyl chloride) (PVC) with nitrile‐butadiene rubber (NBR), PVC with pendent N,N‐diethyldithiocarbamate groups (PVC‐SR) was prepared from the reaction of PVC with sodium SR in butanone. The PVC‐SR was self‐crosslinked and the PVC‐SR/NBR blend was cocrosslinked under heating at 170°C. The effect of the degree of functionality of PVC‐SR on the torque, gel content, glass‐transition temperature, and tensile properties was investigated. The results showed that the crosslinking reaction did not occur for PVC, NBR, or the PVC/NBR blend. Introducing the SR groups into PVC caused the crosslinking reaction to occur and the high gel contents of the crosslinked samples were obtained in 15 min. The degree of crosslinking increased with the degree of functionality of PVC‐SR. The mechanism of the crosslinking reaction was discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 634–638, 2001     

Chemical recycling of poly(vinyl chloride): Application of partially dehydrochlorinated poly(vinyl chloride) for producing a chemically modified polymer

Poly(vinyl chloride) (PVC) pipes were chemically modified to produce a sulfonated polymer with dehydrochlorinated PVC samples as intermediates. Two intermediates were formed: (1) partially dehydrochlorinated PVC with long sequences of conjugated double bonds and (2) the product of the partial dehydrochlorination of PVC and the nucleophilic substitution of chlorine by hydroxyl groups. The IR spectra showed that the dehydrochlorinated samples were heterogeneous materials, showing different proportions of elimination products, hydroxyl substitution, and partial oxidation. Samples dehydrochlorinated with poly(ethylene glycol) with a molecular weight of 400 g/mol for 24 h and 15 min showed the highest sulfonation yield, which was related to the sulfonation mechanism occurring predominantly because of the presence of hydroxyl groups in a mixture of vinyl alcohol and vinyl chloride units. The sulfonation was confirmed by the presence of a medium‐intensity band at 1180 cm^?1, assigned to sulfonic groups. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Contributions to characterization of poly(vinyl chloride)–lignin blends

The present study evaluates the impact of blending organosolv and kraft lignins, which are natural polymer by‐products in the pulp and paper industry, with plasticized poly(vinyl chloride) (PVC) in flooring formulations. Also examined is the impact of replacing dioctyl phthalate, a PVC industry general‐purpose plasticizer, with diethylene glycol dibenzoate (Benzoflex 2‐45), tricresyl phosphate (Lindol), or alkyl sulfonic phenyl ester (Mesamoll) in these formulations. The influence of the different types of lignins and plasticizers on the processibility, thermal, and mechanical properties of the blends is discussed. These properties demonstrate that partial replacement of PVC (20 parts) with different lignins is feasible for some formulations that can be successfully used as matrices for a high level of calcium carbonate filler in flooring products. In addition, the data demonstrate that the presence of certain plasticizers, which interfere with the intramolecular interactions existing in lignins, may allow the lignin molecules to have more molecular mobility. The morphology and the properties of PVC plasticized lignin blends are strongly influenced by the degree and mode of the lignin plasticization and its dispersion within the PVC matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2732–2748, 2006     

Electrical properties and transport conduction mechanism of nitrile rubber/poly(vinyl chloride) blend

The current–voltage characteristics of acrylonitrile butadiene rubber (NBR)/poly(vinyl chloride) (PVC) blends are studied as a function of sample temperature and PVC content. These samples showed ohmic behavior up to (225 V), after this value the behavior become SCLC (space charge limited conduction). The results obtained show that the charge carriers are generated by Richardson–Schottky emission from the electrode as well as from trapped ionic impurities at high fields. The activation energy of the prepared samples was calculated by using Arrhenius equation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Permeability of PEEK to carbon dioxide

Sorption and diffusion of carbon dioxide were measured in amorphous and crystalline poly(aryl-ether-ether-ketone) or PEEK, at different temperatures. The sorption follows Henry's law at all the investigated temperatures, and the reduction of sorption in the crystalline sample corresponds to the reduction of the amorphous phase as derived from X-rays. Due to a more tortuous path, the diffusion parameter in the crystalline sample is lower than in the amorphous one, whereas the activation energy of the diffusion process is similar for both the samples. The permeability to carbon dioxide was very low, comparable, or lower than other rigid polymers. © 1994 John Wiley & Sons, Inc.     

Amphiphilic poly(vinyl chloride)‐g‐poly[poly(ethylene glycol) methylether methacrylate] copolymer for the surface hydrophilicity modification of poly(vinylidene fluoride) membrane

In this study, a comblike amphiphilic graft copolymer containing poly(vinyl chloride) (PVC) backbones and poly(oxyethylene methacrylate) [poly(ethylene glycol) methylether methacrylate (PEGMA)] side chains was facilely synthesized via an atom transfer radical polymerization method. Secondary chlorines in PVC were used as initial sites to graft a poly[poly(ethylene glycol) methylether methacrylate] [P(PEGMA)] brush. The synthesized PVC‐g‐P(PEGMA) graft copolymer served as an efficient additive for the hydrophilicity modification of the poly(vinylidene fluoride) (PVDF) membrane via a nonsolvent‐induced phase‐inversion technique. A larger pore size, higher porosity, and better connectivity were obtained for the modified PVDF membrane; this facilitated the permeability compared to the corresponding virgin PVDF membrane. In addition, the modified PVDF membrane showed a distinctively enhanced hydrophilicity and antifouling resistance, as suggested by the contact angle measurement and flux of bovine serum albumin solution tests, respectively. Accordingly, the PVC‐g‐P(PEGMA) graft copolymer was demonstrated as a successful additive for the hydrophilicity modification, and this study will likely open up new possibilities for the development of efficient amphiphilic PVC‐based copolymers for the excellent hydrophilicity modification of PVDF membranes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of biobased plasticizers on thermal,mechanical, and permanence properties of poly(vinyl chloride)

Phthalates can be replaced by other harmless and environmentally friendly plasticizers, such as isosorbide diesters (ISB), and epoxidized sunflower oil (ESO), which has been proved an efficient stabilizer for poly (vinyl chloride) (PVC) in helping to prevent degradation during processing. Formulations based on PVC with different amounts of ISB, ESO, and di‐(2‐ethylhexyl) phthalate (DEHP) from 0 to 60 parts by weight per hundred parts of resin were realized. To make PVC flexible with partial amounts of the debated phthalates as plasticizers, we use a combination of DEHP, ISB, and ESO. Effects of these two biobased plasticizers, ISB and ESO, and their mixture with DEHP on thermal stability by measuring discoloration degrees and thermal gravimetric analysis, on mechanical properties such tensile strength, elongation at break, and hardness, were characterized. Plasticizer permanence properties of PVC compounds were studied. Studies showed that processibility and flexibility were improved by the addition of a plasticizer system (ISB, ESO, and DEHP). An increase in the content of ISB and/or ESO increased thermal and mechanical properties, whereas compositions with ternary compositions of ISB/ESO/DEHP (15/15/30) exhibited the best performance properties. J. VINYL ADDIT. TECHNOL., 20:260–267, 2014. © 2014 Society of Plastics Engineers     

The Effect of Epoxidized Sunflower Oil on the Miscibility of Plasticized PVC/NBR Blends

Blends of plasticized poly(vinyl chloride) (PVC) with several ratios of nitrile rubber (NBR) were studied. The effects of epoxidized sunflower oil (ESO) in combination with di-(2-ethylhexyl)phthalate (DEHP) in the PVC blends on the tensile strength, elongation, hardness, and dynamical mechanical analysis (DMA) were studied. The modulus and hardness results revealed that the addition of ESO to the blend favors the miscibility of PVC and NBR. The PVC/NBR/(DEHP-ESO) blends behave as a compatible system as is evident from the single T _g observed in DMA. The moderate level broadening of the T _g zone in blends is due to the presence of ESO in the plasticizer system. Blends of plasticized PVC and nitrile rubber showed promising properties. The ESO is suitable to partially replace DEHP in PVC/NBR blends.     

Improved properties of molecular composite of nitrile rubber and poly (p-phenylene terephthalamide) by blending with poly (vinyl chloride)

Summary Nitrile rubber (NBR) was reinforced by poly(p-phenylene terephthalamide) (PPTA) with a coprecipitation method from a common solvent of them. PPTA was converted to N-sodium PPTA with sodium hydride in DMSO, forming homogeneous solution. DMF dissolves NBR. Both solutions were blended to form an isotropic solution. The precipitant was NBR reinforced by PPTA which was regenerated from N-sodium PPTA at coagulation as reported previously. The molecular composite thus obtained was mill-blended with poly(vinyl chloride) (PVC) in order to enhance solvent resistant property. The vulcanized composite of NBR/PVC reinforced by PPTA showed higher modulus, higher strength and more improved solvent resistance than the gum stock and the black stock of NBR/PVC. The properties of the molecular composite containing 5phr PPTA found approximately comparable to those of the black stock of NBR/PVC with 30–40phr ISAF carbon black.On Leave from Japan synthetic Rubber Co., Ltd., Higashi-yurigaoka, Assao-ku, Kawasaki 215, Japan     

Benzyl ester of dehydrated castor oil fatty acid as plasticizer for poly(vinyl chloride)

The poly(vinyl chloride) (PVC) industry plays an important role in today's total plastics industry. The major volume of PVC is used as soft and plasticized PVC. PVC applications consume approximately 80% of the total production of plasticizers. Most of the common plasticizers are aromatic esters of phthalic acid. In the majority of countries, phthalate plasticizers are banned due to their carcinogenic properties. The concern raised about toxicity led to a large demand for bio‐based non‐toxic plasticizers. Hence, there is an increasing interest in replacing the phthalate plasticizers with those produced from simple bio‐based materials. Dehydrated castor oil fatty acid (DCOFA) is a renewable resource which can be esterified and used as an environment friendly plasticizer for PVC. Benzyl ester (BE) was prepared by reacting DCOFA with benzyl alcohol in the presence of catalyst at 170–180 °C. Esterification was further confirmed by acid value, hydroxyl number, ¹H NMR and Fourier transform IR spectroscopy. The modified plasticizer was used in various proportions as a co‐plasticizer in PVC for partial replacement of dioctyl phthalate (DOP). With an increase in the proportion of BE in PVC samples, a good plasticizing performance was observed. The incorporation of BE also resulted in a reduction in viscosity and viscosity pick‐up and improved mechanical, exudation, thermal degradation and chemical resistance properties. The presence of BE showed a reduction in the whiteness index due to presence of conjugated double bonds in the structure. The results of DSC, XRD and Shore hardness studies showed no significant variation in properties compared with those of DOP‐plasticized sheets and thus we can conclude that BE can be used as a co‐plasticizer in PVC. © 2013 Society of Chemical Industry     

Microwave‐absorbing performance and mechanical properties of poly(vinyl chloride)/acrylonitrile–butadiene rubber thermoplastic elastomers filled with multiwalled carbon nanotubes and silicon carbide

Poly(vinyl chloride) (PVC)/acrylonitrile–butadiene rubber (NBR) were mixed with multiwalled carbon nanotubes (MWCNTs) and silicon carbide (SiC) to prepare microwave‐absorbing composites. The complex permittivity, direct‐current (dc) conductivity, microwave‐absorbing performance, morphology, and mechanical properties of the composites were studied. The real and imaginary parts of the permittivity of the composites increased with increasing MWCNT content. The premixing of the MWCNTs with PVC was more beneficial to the dispersion of MWCNTs; this led to a higher dc conductivity and permittivity and better microwave‐absorbing performance than the premixing of MWCNTs with NBR for the PVC/NBR/MWCNT composites. The PVC/NBR/MWCNT composites had a minimum reflection loss (RL_min) of ?49.5 dB at the optimum thickness of 1.96 mm. The efficient microwave absorption of the PVC/NBR/MWCNT composites was due to a high dielectric loss and moderate permittivity. The incorporation of SiC into the PVC/NBR/MWCNT composites increased the real and imaginary parts of permittivity of the composites. When the SiC content was 70 phr, RL_min decreased to ?34.9 dB at a thickness of 3 mm. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of di-(2-ethylhexyl) phthalate (DEHP) released from laboratory equipments

Di-(2-ethylhexyl) phthalate (DEHP) is a plasticizer used in polyvinyl chloride (PVC) manufacturing and is an endocrine disrupter. DEHP was released from laboratory tubing and resins during solvent extraction of natural plants to isolate skin depigmenting compounds. Contamination of DEHP significantly interfered with the purification of depigmenting compounds, since DEHP showed high depigmenting activity (IC₅₀=24 μM) and did not show cell toxicity up to 20 μM. Release of DEHP depended on the composition of tubing materials and solvents used in the extraction process. This result provides practical information for the proper selection of laboratory materials and solvents especially in the extraction and isolation of skin depigmenting compounds for cosmetic ingredients.     

Layered double hydroxide/NaSb(OH)6–poly(vinyl chloride) nanocomposites: Preparation,characterization, and thermal stability

A novel layered double hydroxide/NaSb(OH)₆‐based nanocomposite (Sb‐LDH) has been prepared via intercalation of thio‐antimonite (SbS₃^3?) and reconstruction of LDH using Mg‐Al LDH as precursors. It is composed of LDH nanolayers with thickness of 25 nm and NaSb(OH)₆ nanoparticles with diameter of 3–25 nm. The presence of NaSb(OH)₆ will decrease the decomposition intensity and hinder the decomposition of Mg‐Al LDH because of the potential synergetic effect. When applied to poly(vinyl chloride) (PVC) composites, both Mg‐Al LDH and Sb‐LDH can enhance the thermal stability and increase the decomposition temperature of PVC. Compared with Mg‐Al LDH, Sb‐LDH results in higher decomposition temperatures and whiteness and higher initial and long‐term stabilities due to the presence of NaSb(OH)₆, which can react with HCl and coordinate with Cl in the PVC chains. Because Mg‐Al LDH will accelerate the dehydrochlorination of PVC driving by the Lewis acid such as AlCl₃, the thermal stability of PVC decreases with increasing nanofiller loading. When 1 wt % Sb‐LDH was added, the color change time and Congo red time of PVC composites are 140 min and 154 min, respectively. With enhanced thermal stabilization, this novel LDH nanocomposite could gain promising application in thermal stabilizer for PVC resins. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reinforcement on the mechanical‐, thermal‐, and water‐resistance properties of the wood flour/chitosan/poly(vinyl chloride) composites by physical and chemical modification

In this study, we aimed to physically and chemically modify wood flour (WF)/chitosan (CS) mixtures to reinforce the mechanical‐, thermal‐, and water‐resistance properties of WF/CS/poly(vinyl chloride) (PVC) composites with a three‐step modification process. This was a vacuum‐pressure treatment of sodium montmorillonite, inner intercalation replacement of organically modified montmorillonite, and surface grafting of glycidyl methacrylate (GMA). The untreated and modified mixtures were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy–energy‐dispersive spectroscopy, thermogravimetric analysis, and contact angle measurement. Meanwhile, the mechanical strengths and water absorption of WF/CS/PVC were estimated. The results indicate that the samples had a better performance after they were modified by montmorillonite (MMT) + GMA than when they were modified by only MMT. MMT and GMA showed a very synergistic enhancement to the mechanical‐, thermal‐, and water‐resistance properties of the WF/CS/PVC composites. Specifically, the maximum flexural and tensile strengths were increased by 10.59 and 12.28%, respectively. The maximum water absorption rate was decreased by 61.99%, and the maximum degradation temperature was delayed to the higher value from 314.3 and 374.9°C in the untreated sample to 388.8 and 412.8°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40757.     

Modification of Theoretical models to predict mechanical behavior of PVC/NBR/organoclay nanocomposites

Organo‐modified nanoclay (Cloisite 30B) was added via direct melt mixing to the acrylonitrile butadiene rubber/poly(vinyl chloride) (PVC/NBR) to fabricate polymer blend/clay nanocomposites. The states of nano‐fillers dispersion were investigated by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). From the morphological study of nanocomposites, it is concluded that exfoliated morphology is obtainable by introduction of 2.5 vol % of nanoclay. The effect of nano‐filler volume content on the mechanical properties of PVC/NBR matrix reinforced by Cloisite 30B was investigated by tensile test. Experimental results show that the Young's modulus and tensile strength of composites can significantly improved with a small amount of nanofiller. Moreover, to investigate the stress–strain behavior of NBR/PVC nanocomposites, seven constitutive models such as Arruda–Boyce, Mooney–Rivilen, Marlow, second order of polynomial, Van der Waals, and third order Odgen were studied and compared with experimental data. Results showed that Malow and second order polynomial model can be used for nanoclay‐filled compound whereas the other models show more deviation from experimental data. Three micromechanical models named liner rule of mixtures (LROM) and the inverse rule of mixtures (IROM). Halpin–Tsai theory was applied to evaluate the dependence of Young modulus of nanocomposites on volume fraction of nanofiller. Two modifying factors were proposed to evaluate the Young's modulus of nanocomposites which could greatly improve the theoretical prediction obtained from inverse rule of mixtures (IROM) and Halpin–Tsai equation. The modifying factors were introduced by adopting an exponential, power‐law and linear factors in the equation. In order to verify the suitability of the modified models, the ensuing theoretical predictions are compared to the other experimental data available in the literature. Good predictability of the modified models is demonstrated in the results. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3229–3239, 2013     

Evaluation of the effects of biobased plasticizers on the thermal and mechanical properties of poly(vinyl chloride)

Blends were prepared of poly(vinyl chloride) (PVC) with four different plasticizers; esters of aconitic, citric, and phthalic acids; and other ingredients used in commercial flexible PVC products. The thermal and mechanical properties of the fresh products and of the products after 6 months of aging were measured. Young's modulus of the PVC blends was reduced about 10‐fold by an increase in the plasticizer level from 15 to 30 phr from the semirigid to the flexible range according to the ASTM classification, but a 40‐phr level was required for PVC to retain its flexibility beyond 6 months. At the 40‐phr level, tributyl aconitate performed better than diisononyl phthalate (DINP) or tributyl citrate, in terms of lowering Young's modulus, both in the fresh materials and those aged for 6 months. The effects of the four plasticizers on the glass‐transition temperature (T_g) were similar, with T_g close to ambient temperature at the 30‐ and 40‐phr levels in freshly prepared samples and at 40–60°C in those aged for 6 months. The thermal stability of the PVC plasticized with DINP was superior among the group. Overall, tributyl aconitate appeared to be a good candidate for use in consumer products where the alleged toxicity of DINP may be an issue. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1366–1373, 2006     

改性矿物填料增强橡胶/聚氯乙烯共混体系

研究了橡胶、增塑剂、矿物填料和表面处理剂对橡胶／聚氯乙烯(PVC)共混物力学性能的影响,用扫描电镜分析了有机胺类表面处理剂改性高岭土／丁腈橡胶(NBR)／PVC的界面结合状况。结果表明,当NBR用量为30份,邻苯二甲酸二辛酯用量为60份,有机胺类表面处理剂质量分数为3％,填充60份的超细碳酸钙或高岭土或牌号为SMF的蒙脱土时,可得到力学性能较佳的NBR／PVC共混物;不同矿物填料对NBR／PVC共混物的增强作用不同,经有机胺类表面处理剂改性后,以超细碳酸钙、高岭土和蒙脱土SMF的增强效果最为明显。     

Preparation of poly(vinyl chloride) (PVC) ultrafiltration membranes from PVC/additive/solvent and application of UF membranes as substrate for fabrication of reverse osmosis membranes

Ultrafiltration (UF) membranes were prepared from poly(vinyl chloride) (PVC) as main polymer, poly(vinyl pyrrolidone) (PVP) as additive, and 1‐methyl‐2‐pyrrolidone (NMP) as solvent using Design Expert software for designing the experiments. The membranes were characterized by SEM, contact angle measurement, and atomic force microscopy. The performance of UF membranes was evaluated by pure water flux (PWF) and blue indigo dye particle rejection. In addition, the molecular weight cutoff of UF membranes was determined by poly(ethylene glycol) (PEG) rejection. The UF membranes were used as substrates for fabrication of polyamide thin film composite (TFC) reverse osmosis (RO) membranes. The results showed that the model had high reliability for prediction of PWF of UF membranes. Also, increment in PVC concentration caused reduction of PWF. Moreover, at constant PVC concentration and if the concentrations of PVC was lower than 10 wt %, the PWF reduced by increasing the concentration of PVP. However, at PVC concentration higher than 11 wt %, increment in PVP concentration showed increment and reduction of PWF. The PEG rejection results showed that the prepared membranes had UF membranes properties. Finally, the NaCl rejection tests of RO membranes by PVC as substrates indicated that the performance of RO membranes were lower than commercial membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46267.