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     

Synthesis of glycidylethylhexylphthalate and its effects on poly(vinyl chloride) films as a novel plasticizer

To improve the processability and prevent the thermal degradation of poly(vinyl chloride) (PVC), various plasticizers and heat stabilizers have to be compounded. Phthalic plasticizers and metal soap stabilizers are usually used with epoxides as costabilizers. Epoxidized soybean oil (ESO), is one of the most commonly used epoxides because of its typical combined roles as a plasticizer and heat stabilizer in PVC compounds. ESO, however, sometimes causes surface contamination of PVC compounds because saturated fatty acids such as stearic and palmitic acids in soybean oil easily bleed onto the surface. In addition, some ingredients in ESO with hydroxide groups and unreacted double bonds during epoxidization also tend to increase the bleeding of ESO. This is due to their low compatibility with PVC resins. In this study, a novel plasticizer of PVC resins, glycidylethylhexylphthalate (GEHP), was synthesized, and its performance was evaluated. GEHP was designed to act as a plasticizer like normal phthalic plasticizers and to act as a heat stabilizer like ESO. Through the addition of epoxy groups in phthalic compounds, the resistance to bleeding was improved, and the plasticizing and heat‐stabilizing effects on the PVC compounds were preserved. Soft PVC films were prepared with GEHP. The mechanical properties, thermal stability, and bleeding properties of the films were investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1347–1356, 2005     

Effects of epoxidized sunflower oil on the mechanical and dynamical analysis of the plasticized poly(vinyl chloride)

Epoxidized soybean oil (ESBO), is one of the most commonly used epoxides because of its typical combined roles as a plasticizer and heat stabilizer. In this study, a novel plasticizer of poly(vinyl chloride) (PVC) resins, epoxidized sunflower oil (ESO), was synthesized, and its performance was evaluated. ESO was designed to act as a coplasticizer and a heat stabilizer like ESBO. ESO is used as organic coplasticizer for plasticized PVC containing Ca and Zn stearates as primary stabilizers and stearic acid as lubricant. Di‐(2‐ethylhexyl) phthalate (DEHP), a conventional plasticizer for PVC, was partially replaced by ESO. Mechanical properties (tensile and shore D hardness) were investigated. The performance of ESO to ESB0 (20 g) for comparison, indicated that ESO could be used as secondary plasticizer for PVC in combination with DEHP. All mechanical and dynamical properties of plasticized PVC sheets varied with the oxirane oxygen of the ESO. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dialkyl furan‐2,5‐dicarboxylates,epoxidized fatty acid esters and their mixtures as bio‐based plasticizers for poly(VInylchloride)

Dialkyl furan‐2,5‐dicarboxylates and epoxidized fatty acid esters (EFAE) of varying molecular weights and volatilities, as well as their mixtures, were investigated as alternative plasticizers for poly(vinylchloride) (PVC). The EFAE utilized were epoxidized soybean oil (ESO) and epoxidized fatty acid methyl ester (e‐FAME). All plasticizers were compatible with PVC, with plasticization efficiencies usually increasing with decreasing molecular weights of the plasticizers (except in the case of ESO, which was remarkably effective at plasticizing PVC, in spite of its relatively high molecular weight). In comparison with phthalate and trimellitate plasticizers, the alternatives generally yielded improved balance of flexibility and retention of mechanical properties after heat aging, with particularly outstanding results obtained using 30?50 wt % e‐FAME in mixtures with diisotridecyl 2,5‐furandicarboxylate. Although heat aging characteristics of the plasticized polymer were often related to plasticizer volatilities, e‐FAME performed better than bis(2‐ethylhexyl) 2,5‐furandicarboxylate, and bis(2‐ethylhexyl) phthalate of comparatively higher molecular weights. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42382.     

Bis(2‐ethylhexyl) succinate in mixtures with epoxidized soybean oil as bio‐based plasticizers for poly(vinylchloride)

Mixtures of bis(2‐ethylhexyl) succinate and epoxidized soybean oil (ESO) have been evaluated as bio‐based plasticizers for poly(vinylchloride). The rate of absorption of the bioplasticizers and their mixtures in the polymer was fast and, unlike that of petroleum‐derived plasticizers, did not vary significantly with molecular weight. These bio‐derived plasticizers and their mixtures were compatible with the polymer even at high loadings. The succinate was the most volatile and efficient plasticizer, but on heat aging of the polymer compositions, it also had the greatest deleterious effects. Diffusion coefficients and apparent activation energies of formulations containing bioplasticizer mixtures were controlled by the more volatile succinate. Mixtures comprising up to 50 wt% of the succinate yielded acceptably high‐tensile properties after thermal aging as well as better plasticization efficiency than the epoxy bioplasticizer. Although the succinate resulted in inferior volume resistivity of the polymer compositions, improvements were obtained with increasing proportions of the epoxidized derivative in plasticizer mixtures. Melt state viscosity‐shear rate curves of compositions containing dioctyl succinate (DOS) were similar to those made with two of the petroleum‐derived plasticizers, but a DOS/ESO mixture yielded extended non‐Newtonian behavior at low‐shear rates. POLYM. ENG. SCI., 55:634–640, 2015. © 2014 Society of Plastics Engineers     

Characterization of 1,5‐pentanediol dibenzoate as a potential “green” plasticizer for poly(vinyl chloride)

1,5‐Pentanediol dibenzoate (PDDB) was evaluated as a potential “green” plasticizer for poly(vinyl chloride) (PVC) at concentrations ranging between 20 and 80 parts by weight per hundred parts of resin. The results of glass transition temperature (T_g) and tensile tests of PDDB blends with PVC were compared with those for blends of the commercial plasticizers di(2‐ethylhexyl) phthalate (DEHP), di(ethylene glycol) dibenzoate (DEGDB), and di(propylene glycol) dibenzoate (DPGDB) in PVC. The depression in T_g and the tensile properties were comparable for a PDDB/PVC blend at a fixed composition to those of blends with DEHP, DEGDB, and DPGDB. The PDDB was subjected to biodegradation using co‐metabolism by the common soil bacterium Rhodococcus rhodochrous (ATCC 13808). After 16 days of growth, nearly all of the PDDB was degraded, and only small amounts of transient, unidentified metabolites were observed in the growth medium during the experiment. J. VINYL ADDIT. TECHNOL., 2009. © 2009 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.     

Hybrid sol gel coating: A solution to prevent interactions between plasticized poly(vinyl chloride) and injectable drugs?

During the infusion of drugs with medical devices in plasticized poly(vinyl chloride) (PVC) release of plasticizers in the injectable solution and/or sorption of drugs on PVC may occur. Thus, patient safety and/or effectiveness of his therapy may be altered. In this study, we assessed the efficiency of a sol gel hybrid coating in preventing plasticizers' release (di‐(2‐ethylhexyl) phthalate (DEHP)) from PVC matrix and drug sorption into PVC. Remaining concentrations of drugs and plasticizer's concentration released after migration tests were assessed by liquid chromatography. Migration processes were followed by Fourier Transform Infrared – Attenuated Total Reflectance (FTIR‐ATR) spectroscopy and PVC surface changes were characterized by scanning electron microscopy (SEM). An evaluation of the mechanical properties of both uncoated and coated polymer was done. The hybrid coating protects PVC from plasticizers leaching. Sorption of drugs tested is also limited. However, the protection against plasticized PVC interactions isn't optimal, probably due to a degradation of the layer, as shown on SEM microphotographs. Furthermore improvements might provide an efficient barrier to advert risks impaired to PVC interactions, to provide patient care safety. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40145.     

Succinate-based plasticizers: Effect of plasticizer structure on the mechanical and thermal performance of poly(vinyl chloride) plastic formulations

A new family of succinate-based plasticizers, consisting of molecules with a linear alkyl chain capped with n-alkyl succinates on both ends, was evaluated as potential bio-based plasticizers for stiff polymers. The influence of the central and side alkyl chain lengths on the mechanical and thermal properties as well as the migration behavior of poly(vinyl chloride) (PVC)/plasticizer blends was evaluated. The central chain length had the greatest influence on plasticizer performance, with shorter chains leading to blends with higher stress at break and surface hardness, whereas long chains produced softer blends. An optimum chain central length of five carbon atoms was observed, with longer chains leading to reduced compatibility and exudation of the plasticizer at higher plasticizer concentrations. The entire family of plasticizers performed comparably or better than the commercial plasticizer di(2-ethylhexyl) phthalate (DEHP) when incorporated into the blend at concentrations of 20–60 parts per hundred resin (phr). Overall, the succinate-based plasticizers/PVC blends all exhibited equal or improved tensile properties (by up to 77%), surface hardness (reduced by up to 43%), glass transition temperature (reduced by up to 11°C), and migration into organic media (reduced by up to 38%) when compared with blends with DEHP at 40 phr.     

Novel branched poly(ɛ‐caprolactone) as a nonmigrating plasticizer in flexible PVC: Synthesis and characterization

A series of hyperbranched poly(?‐caprolactone) (HPCLs, denoted as D_X) with different molecular weights were synthesized by the copolymerization of GPCL (PCL initiated by glycidol) and succinic anhydride. The chemical structure of D_X was characterized by ¹H‐NMR gel permeation chromatography and inherent viscosity, and D_X was used as the plasticizer for poly(vinyl chloride) (PVC) compared to traditional plasticizer di‐(ethylhexyl) phthalate (DEHP). The thermal properties, morphology, mechanical properties, and migration stabilities of PVC films were explored with differential scanning calorimetry, thermogravimetric analysis, scanning electron microscope, tensile, and migration tests. PVC/D₁ exhibited the best plasticization efficiency up to 107%, with enhanced tensile strength (18.5 MPa) and ultimate elongation (416%) compared to PVC/DEHP (11.5 MPa and 375%, respectively). PVC/D₁ exhibited remarkably high plasticization efficiency as compared to PVC/DEHP at a plasticizer concentration of PVC below 40 wt %. Moreover, the migration test for PVC/D_X films exhibited minimal plasticizers migration even at very harsh conditions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46542.     

助剂对聚氯乙烯软塑制品相容性、迁移性、耐候性的影响与分析

生产聚氯乙烯软塑制品,增塑剂占有较大的质量比例,加工过程必须使用热稳定剂。生产具有耐候功能的聚氯乙烯软制品,要选择适当、适量的光稳定剂、抗氧剂。增塑剂、热稳定剂、光稳定剂的相容性、迁移性以及品种和添加量,对于聚氯乙烯软塑制品的物理机械性能和耐候性有较大影响。     

Synthesis and application of an alternative plasticizer Di(2‐Ethylhexyl)‐1,2‐cyclohexane dicarboxylate

Cyclohexane dicarboxylic acid esters are environmentally friendly and non‐toxic plasticizers, and have similar performance with phthalates which have potential toxicity to human health. In this article, di(2‐ethylhexyl)‐1,2‐cyclohexane dicarboxylate (DEHCH) was synthesized via esterification between hexahydrophthalic anhydride (HHPA) with iso‐octanol by using concentrated sulfuric acid as a catalyst. The effects of reaction parameters on esterification were studied by investigating the temperature, reaction time, molar ratio of iso‐octanol‐to‐HHPA, and catalyst content. Conversions of HHPA to esters were determined. Functional group analysis was conducted by using FTIR and ¹H‐NMR spectroscopy. PVC compounds after addition of the synthesized plasticizer DEHCH presented similar plasticizing performance with DEHP and DINCH, as demonstrated by comparisons of the results of mechanical properties, transparency, and volatilization and migration tests obtained for plasticized PVC compounds. DEHCH can also be considered as an alternative plasticizer for DEHP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39763.     

Application of new oligomeric plasticizers based on waste poly(ethylene terephthalate) for poly(vinyl chloride) compositions

In this study, chemical recycling products of waste poly(ethylene terephthalate) with oligoesters were used as new plasticizers for poly(vinyl chloride) (PVC). The preparation conditions of the dry blend mixtures of the suspension PVC containing synthesised plasticizers were similar to the conditions of the preparing mixtures with commercial plasticizers. The plasticization efficiency of PVC plasticizers was then examined by analysis of the mechanical, physical and chemical properties, as well as the thermal resistance and migration of plasticizer molecules from polymer matrix. Test results proved that compositions with synthesised oligomeric plasticizers possessed similar or better properties than those containing commercial oligomeric plasticizers and much better properties than those having monomeric plasticizers. Thermal stabilities of the proposed plasticizers were higher than those of the commercial plasticizers either monomeric (bis(2-ethylhexyl)phthalate) or oligomeric, despite the fact that the synthesised oligoesters did not contain any antioxidant. The best properties, especially low volatility, very good mechanical properties, low migration were resulted of the transesterification of the waste PET with oligoesters based on adipic acid, triethylene glycol and 2-ethylhexanol which were selected as plasticizers synthesised on the technical scale. The tested plasticized PVC compositions possessed very good tear resistance, tensile strength, decrease of weight loss after 168 h at 80 °C and low migration. Processing properties of PVC compositions containing these synthesised plasticizers confirmed their effectiveness in these compositions for extrusion process.     

Soil burial degradation of new bio‐based additives. Part II. plasticized poly(vinyl chloride) films

Commercial sunflower oil was epoxidized, and the epoxidized oil (ESO) was used as a new thermal stabilizer for poly(vinyl chloride) (PVC). Plasticized formulations stabilized with ESO and epoxidized soya bean oil as a commercial stabilizer were evaluated for comparison. Two plasticizers were used, dioctyl phthalate and diisononyl adipate. The aging of the PVC samples was investigated in landfill soil for 24 months. The modifications of the structure of the polymer were followed by Fourier, transform infrared spectroscopy. Furthermore, the variations of density and mechanical properties (tensile and Shore D hardness) were considered, and the variations of the mass of the samples, the glass transition temperature (T_g), the molar mass distribution, and the weight loss were followed as a function of duration of soil burial. The morphological changes were tracked by scanning electron microscopy. Results showed that the nature of the plasticizer and heat stabilizer affects the properties of PVC as well as the phenomena of migration and biodegradation. J. VINYL ADDIT. TECHNOL., 19:183‐191, 2013. © 2013 Society of Plastics Engineers     

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.     

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

Effects of three different plasticizers and their blends with dioctyl phthalate (DOP) on thermal stability, flammability, mechanical, electrical, and permanence properties of poly(vinyl chloride) (PVC) compound were studied. Various plasticizers used were DOP, butyl benzyl phthalate (BBP), isodecyl diphenyl phosphate (IDDP), and polybutylene adipate (PBA) at concentrations of up to 40 phr level. Studies showed that processability and softness were improved by addition of BBP. An increase in the content of IDDP increased the electrical and flammability properties, whereas compositions with PBA exhibited the best permanence properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3278–3284, 2003     

Evaluating effects of biobased 2,5‐furandicarboxylate esters as plasticizers on the thermal and mechanical properties of poly (vinyl chloride)

We synthesized 2,5‐furandicarboxylate esters [i.e., dibutylfuran‐2,5‐dicarboxylate, diisoamylfuran‐2,5‐dicarboxylate, and di(2‐ethylhexyl)furan‐2,5‐dicarboxylate] and investigated their potential application as plasticizers of commercial poly(vinyl chloride) (PVC) products. Fourier transform infrared analysis, mechanical tests, scanning electron microscopy investigation, differential scanning calorimetry analysis, dynamic mechanical thermal analysis, thermogravimetric analysis (TGA), melt flow rate (MFR) measurement, and plasticizer migration measurements were used to the evaluate the comprehensive properties of the blended products. The results of the tensile tests demonstrate that the blends exhibited antiplasticization and flexible plastic characteristics at 10 and 50 phr in PVC, respectively. Moreover, flexural and impact test data indicate that the three types of blends exhibited a similar tendency: the hardness decreased continuously as the amount of plasticizer increased. Their morphology indicated that all of the plasticizers had good compatibility with PVC. The resulting glass‐transition temperature of the investigated plasticizers was lower than that of pure PVC, and reduction was largest for the plasticizer with the highest molecular weight. TGA revealed that the thermal degradation of blended polymers occurred in three stages and that all of the blends were stable up to 180°C. Finally, the MFRs of all of the specimens indicated that the addition of a higher concentration of lower molecular weight biobased esters resulted in improved fluidity, but these compounds migrated more easily from the blends. Hence, 2,5‐furandicarboxylic acid derived from biomass has potential as a plasticizer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40938.     

Bio-based epoxidised oil for compatibilization and value addition of poly (vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) in recycled blend

The effective utilization of bio-based material, epoxidised soybean oil (ESO), in recycled blend of Poly(vinyl chloride)/Poly(methyl methacrylate) (PVC/PMMA) was considered for the first time in this present investigation. Recycled blend with different concentrations of ESO were prepared via melt blending technique. Resulted blends were characterized by various physiochemical, mechanical and thermal characterizations. Fourier transform infrared (FTIR) analysis indicates reduction in the degradation behaviour of PVC phase present in the PVC/PMMA blend after introduction of ESO into it. The recycled blend with 9 wt% of ESO exhibit superior impact strength than other compositions. The thermal gravimetric analysis of ESO incorporated blend shows improved thermal stability than its parent blend. The DSC analysis shows improved compatibility of recycled blends in presence of ESO. Moreover the scanning electron microscope (SEM) analysis exhibits improved surface morphology with enhanced interfacial adhesion. Thus this study paves way for exploitation of bio derived ESO for value addition of recycled plastics from waste electrical and electronic equipments.     

Migration of additives in simulated landfills and soil burial degradation of plasticized PVC

Commercial sunflower oil was epoxidized, and epoxidized sunflower oil (ESO) was used as a thermal stabilizer for polyvinyl chloride (PVC). Semirigid and plasticized formulations stabilized with ESO were realized. Three plasticizers were used: dioctyle phthalate (DOP), diisodecycle phthalate (DIDP), and diisononyle adipate (DINA). Leaching tests simulating real landfill conditions were performed. The two model leachates selected for laboratory leaching tests were solution of acetic acid and distilled water, respectively, corresponding to simulants for domestic waste leachates and rainfall on wastes deposited in bulk. The leaching tests were carried out at 25 and 50°C during 15 days. The variation of the mass of the samples was followed as a function of time. On the other hand, the ageing of the PVC samples was investigated in a landfill soil for 6 months. The modifications of the structure of the polymer were followed by Fourier transform infrared spectroscopy (FTIR). Furthermore, the variation of density and mechanical properties (tensile and shore D hardness) were considered. The results showed that both nature and content of plasticizer influence the migration of the PVC additives used. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Absorption and migration of bio‐based epoxidized soybean oil and its mixtures with tri(2‐ethylhexyl) trimellitate in poly(vinylchloride)

The efficacy of epoxidized soybean oil (ESO), tri(2‐ethylhexyl) trimellitate, and mixtures thereof as plasticizers for poly(vinylchloride) has been studied. At 80°C, the trimellitate was slower to absorb in this polymer than ESO and was also less soluble, but the former exhibited higher solubility at 120°C. Plasticization efficiencies of stabilized polymeric compositions were similar with ESO and the trimellitate (despite their very different molecular weights). The trimellitate yielded greater mass loss during heat aging of the plasticized compositions, but substituting even minor amounts of it with ESO decreased mass loss synergistically. The trimellitate also resulted in more of an increase in hardness than ESO over time at elevated temperatures, but when aged at 120°C, mixtures of the two surprisingly had more deleterious effects. Thus, although ESO can replace part or all of trimellitates in plasticized PVC, using it as sole plasticizer would be preferable when heat aging performance is a requirement. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41966.