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.     

水滑石在软质聚氯乙烯中的应用研究

研究了环氧大豆油(ESO)、亚磷酸酯(Phosphite)、β二酮(β-diketone)和水滑石(LDHs) 4种辅助稳定剂和钙锌(Ca/Zn)主稳定剂复配对聚氯乙烯（PVC）软制品的热稳定性、力学性能、烟密度等性能的影响。结果表明,与其他辅助热稳定剂相比,LDHs和Ca/Zn稳定剂复配对PVC软制品具有较好的长期热稳定性,并使PVC复合材料的烟密度有所降低。     

PVC用热稳定剂的研究

考察了影响聚氯乙烯(PVC)热稳定性的几种化合物,研究确定了几种稳定剂间的协同作用和较佳复配结果.结果表明:NaOH、Fe3+、过氧化二苯甲酰(BPO)对PVC的热稳定性均具有破坏作用;Ca/Zn与环氧大豆油(ESO)、β-二酮、亚磷酸酯均具有较好的协同作用,较佳的Ca/Zn稳定剂配方为Ca/Zn总量约2.0份、环氧大...     

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     

Concentration dependency of interaction parameter between PVC and plasticizers using inverse gas chromatography

The inverse gas chromatography method was extended to study the concentration dependent Flory–Huggins interaction parameter between poly(vinyl chloride) (PVC) and plasticizers using literature data. For both PVC/polyadipate and PVC/epoxidized soybean oil (ESO) systems, the miscibility was better at the high PVC end. The specific interaction between PVC and plasticizers was estimated from the difference between the experimental results and the enthalpies of mixing predicted by the solubility parameter model. The interaction was negative and skewed toward the high PVC end, and rendered the overall interaction parameter negative at high PVC compositions. Chemical potential was used to determine the phase composition of PVC/plasticizer mixtures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 146–156, 2004     

N⁃乙基哌嗪基邻苯二甲单酰胺酸锌对PVC热稳定性能的影响

以邻苯二甲酸酐、N?乙基哌嗪为原料合成N?乙基哌嗪基邻苯二甲单酰胺酸,再将其与氯化锌反应制备了N?乙基哌嗪基邻苯二甲单酰胺酸锌（ZNEP）,然后将ZNEP分别与季戊四醇、二苯甲酰甲烷（β?二酮）、环氧大豆油和亚磷酸一苯二异辛酯进行复配得到4种复合热稳定剂;采用刚果红试纸法、热老化烘箱法,转矩流变仪法和热重分析仪（TG）研究了不同复合热稳定剂对聚氯乙烯（PVC）静态和动态热稳定性能及热降解过程的影响。结果表明,当ZNEP、季戊四醇复配质量比为1∶2时,PVC样品的热稳定性最好,其静态热稳定时间和动态热稳定时间分别为2 340 s和1 602 s;同时,与不添加热稳定剂的样品相比,其质量损失率为5 %、10 %及质量损失速率最快时对应的温度（T_{5 %}、T_{10 %}、T_max）均表现出了较大程度的提升,说明该复合热稳定剂能有效抑制PVC的热降解。     

Improving gamma radiation resistance: Medical grade,flexible clear PVC compounds

Flexible clear PVC compounds tend to yellow and darken during and after exposure to gamma radiation. This has been an obstacle to their use in the medical market. The purpose of this investigation was to improve the gamma stability of flexible PVC. The variables of interest were resin molecular weight, plasticizer loading, stabilizer type, and choice of antioxidant. By screening resins, plasticizers, stabilizers, lubricants, and antioxidants, a promising candidate formulation was identified and optimized by statistically designed experiment, with hardness added as an additional variable. The criterion for improvement was color change after gamma irradiation, compared with an identical unexposed specimen. Thus, a series of gamma stable formulations were created exhibiting improved post irradiation color stability.     

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.     

Epoxidized jojoba oil as a stabilizer for vinyl chloride containing plastics

Summary Epoxidized jojoba oil has been evaluated as a light and heat stabilizer for vinyl chloride containing plastics and its properties, intercompared with those of other epoxides representative of three major classes of oxirane stabilizers. The results obtained show that epoxidized jojoba oil is a satisfactory thermal and ultraviolet stabilizer for both TCP and DOP plasticized stocks and has no adverse effects on the plasticizer properties of these materials. In general, epoxidized jojoba oil was found to be equivalent to or, in some instances, superior to the other epoxides tested.     

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.     

Thermal stabilization of PVC by “plasticizer thiols”

Various new carboxylate esters containing one or more sulfhydryl groups are shown to be remarkably effective as both thermal stabilizers and plasticizers for poly(vinyl chloride) (PVC). These “plasticizer thiols” function well as primary stabilizers in the absence of metal‐containing additives when they are introduced at either a typical plasticizer level or a conventional stabilizer level. Their syntheses are straightforward and, in some cases, require only an acid‐catalyzed esterification performed with commercially available starting materials. Unlike typical thiols, the purified plasticizer thiols do not have offensive odors when their molecular weights are relatively high.     

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     

Migration of phthalate and non‐phthalate plasticizers out of plasticized PVC films into air

The aim of the present work is to provide information about the migration of phthalate and non‐phthalate plasticizers generally used in flexible polyvinyl chloride (PVC) applications. Plastisols (pastes) were prepared by mixing PVC, plasticizer, and thermal stabilizer. The plasticized PVC (p‐PVC) films are obtained by gelation at 160°C for 15 min. The p‐PVC films were heat treated at 50, 85, 100, 130, and 160°C up to 420 min to follow the mass loss to find out diffusivity of plasticizer out of films into air and to determine related activation energies. The films having di‐octyl terephthalate (DOTP) and di‐isononyl 1,2‐cyclohexanedicarboxylic acid (DINCH) exhibited the lowest mass loss in general, among the phthalate and non‐phthalate plasticizer having p‐PVC films, respectively, as confirmed by FTIR investigation. The same tendency was observed for diffusion coefficients and for the activation energies of migration. The diffusion coefficients were found to be around 3.5 × 10^?18–2.1 × 10^?17 m²/sec for the studied plasticizers in PVC at 50°C and around 4.0 × 10^?15–9.9 × 10^?14 m²/sec at 160°C. The activation energies for 85–160°C interval were determined to be between 70 and 153 kJ/mol (0.72–1.58 eV) for the plasticizers used herein those could be treated as a homologous series as deduced from the related compensation factors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

一类新型环氧增塑剂——环氧植物油酸多元醇酯

介绍了一种新型聚氯乙烯(PVC)增塑剂环氧植物油酸多元醇酯,包括它的合成方法及用其增塑的PVC的物理性质,它与PVC的相容性优于环氧大豆油。在用作PVC的主增塑剂时,被增塑的PVC为力学性能优于用邻苯二甲酸二辛酯(DOP)增塑的同类制品。     

环氧鱼油的性质及其应用研究

采用一步环氧化工艺制得环氧值为4．5％的环氧鱼油,研究环氧鱼油的性质及其在氯乙烯中的作用。研究结果表明：环氧鱼油耐热性高,用于聚氯乙烯中,与金属皂并用有良好的协同稳定作用,作用效果与环氧大豆油相当甚至更好些,可作为聚氯乙烯优良的增塑剂兼稳定剂。     

Influence of additional thermal stabilizers on the reprocessing of postconsumer poly(vinyl chloride) bottles

The addition of heat stabilizers is essential for preventing the degradation of poly(vinyl chloride) (PVC) during its processing. The heat stabilizers consumed in the first run have to be made up before the reprocessing of recycled PVC. In this study, solvent‐cast films, which were prepared from granulated postconsumer PVC bottles mixed with plasticizers and thermal stabilizers, were used. The films were subjected to various heat treatments. No considerable structural change upon heat treatments at 140–160°C was found in IR and differential scanning calorimetry analyses. Polyene formation observed through ultraviolet analysis was not severe, indicating that the added stabilizers worked well in preventing degradation. The weight loss during the heat treatments was attributed partly to the decomposition of PVC and the evaporation of volatile components and mainly to the removal of the solvent upon heating. Although this study was conducted with water bottles that were to be recycled, it may be equally well applied to other similarly formulated PVC‐based materials, such as packaging films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3994–3999, 2003     

环氧大豆油改性透明环氧树脂胶粘剂的研究

以环氧大豆油(ESO)为环氧树脂(EP)的增塑剂、环氧氯丙烷(ECH)和丙烯腈(AN)改性己二胺为固化剂,制得ESO改性EP胶粘剂。探讨了增塑剂种类和含量对EP胶粘剂性能的影响。结果表明:当n(己二胺):n(ECH):n(AN)=1:0.3:1.5、w(ESO)=20%时,相应EP胶粘剂的剪切强度、断裂伸长率和外推起始温度分别比纯EP体系增加了10%、400%和20%;ESO是一种高增韧性、高耐热性的环保型增塑剂,相应EP胶粘剂的透明性、柔韧性和耐高(低)温性俱佳。     

低温热塑性改性氯醋树脂的研究

对氯醋树脂进行改性以得到具有较低软化点、能用于外科矫形材料的低温热塑性材料。采用共混方式将氯醋树脂、热稳定剂、增塑剂及润滑剂熔合在一起。结果表明。二月桂酸丁基锡用作主热稳定剂，硬脂酸锌和硬脂酸钙作为辅助热稳定剂可以有效延缓氯醋村脂的降解。以DOP（邻苯二甲酸二辛酯）为主增塑剂，ESBO（环氧大豆油）为助增塑剂可以调控树脂的软化点。采用最佳配方可以制得软化点为55℃左右的低温热塑性改性氯醋树脂材料。     

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