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.     

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.     

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.     

Bio-based Epoxy Resins from Epoxidized Plant Oils and Their Shape Memory Behaviors

In this study, bio‐based epoxy materials containing functionalized plant oil, such as epoxidized soybean oil (ESO) and epoxidized linseed oil (ELO), were processed with 4‐methylhexahydrophthalic anhydride (MHPA) as a curing agent. In the presence of tetraethylammonium bromide, the curing reaction of epoxidized plant oil and MHPA proceeded at 130 °C to give transparent plant oil‐based epoxy materials. The resulting bio‐based epoxy materials exhibited relatively soft and flexible characters, due to the aliphatic chains of plant oil. The thermal and mechanical properties of the ESO/MHPA polymers depended on the feed molar ratio of anhydride to oxirane. The mechanical properties such as tensile strength and Young's modulus of the ELO/MHPA polymer increased, compared with those of the ESO/MHPA polymer. The glass transition temperature of the ELO/MHPA polymer was higher than that of the ESO/MHPA polymer, because of the high oxirane number of ELO. Furthermore, the ELO/MHPA polymer showed excellent shape memory property.     

An efficient plasticization method for poly(lactic acid) using combination of liquid‐state and solid‐state plasticizers

A combined use of solid plasticizer [poly(ethylene glycol), PEG] with a nominal M_w of 2000 g/mol and liquid plasticizer (epoxidized soybean oil, ESO) for plasticizing poly(lactic acid) (PLA) is proposed in this study. This plasticization method brought an obvious improvement in the melting flowability of the modified PLA, which has been verified by a lower balance torque during blending and a four times increase in the melt flow index compared to neat PLA. Meanwhile, the brittleness of this glassy polymer was also improved significantly; all composites with different contents of combined plasticizers displayed an obvious yield stage and toughness fracture surfaces. The mechanisms of the plasticizing effects were investigated by polarizing optical microscopy and scanning electron microscopy. The PLA/ESO/PEG blends formed a complex reinforcement structure. ESO existed as tiny droplets and uniformly dispersed in the PLA spherulites, and strip‐shaped PEG accumulated along the boundaries of interspherulites. The combined use of these two plasticizers, a liquid one and a solid one, had an excellent effect on plasticizing PLA, not only on melt flowability but also on mechanical properties. Thus, the application areas for PLA could be further expanded, such as melt blowing and melt extrusion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46669.     

UV‐curable pressure‐sensitive adhesives derived from functionalized soybean oils and rosin ester

Functionalized plant oils such as epoxidized soybean oil (ESO) are widely used in plastic industries as additives and are available for more value‐added applications. Pressure‐sensitive adhesive (PSA) derived from petroleum feedstocks has a huge market ranging from tapes to packaging. Here we show a sustainable PSA derived from ESO/dihydroxyl soybean oil (DSO)/rosin ester (Sylvalite) via UV‐initiated copolymerization. The ether crosslinks derived from cationic polymerization of ESO and copolymerization between ESO and DSO (or rosin ester) were demonstrated using ¹H NMR, 2D ¹H–¹H COSY NMR, electrospray ionization mass spectrometry and thermal analyses (differential scanning calorimetry and thermogravimetric analysis). The PSA was formulated by modulating the ratio of ESO/DSO/rosin ester to achieve high performance. At a UV dose of 5.1–5.4 J cm^?2 and 0.3–3% (w/w) of a photoinitiator, i.e. [4‐(2‐hydroxy‐1‐tetradecyloxy)‐phenyl]phenyliodonium hexafluoroantimonate, the PSA at a ratio (by weight) of 1:1:0.7 (ESO/DSO/rosin ester) recorded the highest peel and loop tack strength, which was comparable to a commercial PSA, Scotch Magic Tape, and showed much stronger shear strength (>30 000 min) than the commercial tape (10 000 min). The high‐shear rheological behavior and excellent thermal stability of the PSA were also demonstrated. © 2012 Society of Chemical Industry     

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     

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.     

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     

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     

Curing and mechanical characterization of a soy‐based epoxy resin system

A potentially inexpensive alternative epoxy resin system based on soybean oil has been developed for polymer composite applications. Epoxidized methyl soyate (EMS) and epoxidized allyl soyate (EAS) have been synthesized at the University of Missouri–Rolla. These materials consist of mixtures of epoxidized fatty acid esters. The epoxidized soy‐based resins provide better intermolecular crosslinking and yield materials that are stronger than materials obtained with commercially available epoxidized soybean oil (ESO). The curing behavior and glass transition have been monitored with differential scanning calorimetry. Neat resin test samples have been fabricated from resin systems containing various amounts of EMS, EAS, and ESO. Standardized tests have shown that the addition of EAS enhances the tensile and flexural properties of the base epoxy resin system. Therefore, epoxidized soy ester additives hold great potential for environmentally friendly and lower cost raw materials for the fabrication of epoxy composites for structural applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3513–3518, 2004     

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。     

Studies on carboxy‐terminated liquid natural rubber in NBR

Maleic anhydride was chemically attached to depolymerized natural rubber by a photochemical reaction. The product Carboxy Terminated Liquid Natural Rubber (CTNR) was characterized by ¹H‐NMR, IR, GPC, and TGA. The efficiency and permanence of CTNR were compared with conventional plasticizers in NBR vulcanizates. This polymeric plasticizer was found to be less volatile and more resistant to oil extraction. The vulcanizates showed improved aging resistance compared to vulcanizates containing conventional plasticizers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 261–267, 2002; DOI 10.1002/app.10322     

Epoxidized vegetable oil and bio‐based materials as PVC plasticizer

Phthalate esters received a considerable attention owing to its various applications and the harmful health effects resulting from phthalate exposure; thus, finding an alternative to phthalate derivatives became a necessity. Phthalate esters are commonly used as plasticizer in polymer formulation; in particular for poly(vinyl chloride) (PVC) formulation. According to the researches in the last 18 years, epoxidized vegetable oils are one of the alternatives that are strongly encouraged to substitute phthalate esters since they were proven to be valid in various applications, eco‐friendly and sustainable resource. However, most of the production practices for epoxidized vegetable oil are via conventional epoxidation that concentrates on a catalyst that is homogeneous and non‐reusable. This type of catalyst, however, causes several problems later in the process. Therefore, the selective epoxidation of vegetable oils process requires new catalytic systems that are more aligned with the green chemistry principles. This article reviews the harmful health effects associated with the exposure to phthalate esters products, explains the usage of oleochemicals resources as a substitute to phthalate esters and describes different approaches for the epoxidation of vegetable oils. Finally, it draws attention to the usage of epoxy and bio‐based compounds as plasticizers in PVC manufacturing. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46270.     

Renewable (waste) material based polyesters as plasticizers for adhesives

The aim of the presented work was to replace phthalate based plasticizers with environmentally friendly materials to provide similar properties for poly(vinyl acetate) (PVAc) adhesives.Polyesters synthesized from the liquefied wood (PE-LW) and depolymerized polyethylene terephthalate (PE-PET) were used as renewable raw materials and evaluated as plasticizers used in PVAc dispersion adhesives for flooring applications. As a reference plasticizer, 1,2,3-triacetoxypropane was used.PVAc adhesives were evaluated with respect to solids content, viscosity, glass transition temperature (T_g), tensile shear strength and binding strength.TGA analysis showed significant differences between the thermal stability of added polyesters and the commercial plasticizer. Samples prepared with PE-PET exhibit the best thermal stability even with an increase of 25% PE-PET. The addition of coalescing agents or plasticizers leads to a temporary softening of the PVAc polymer and a decrease in the glass transition temperature.The type and content of plasticizer have great influence on wood–wood binding strength, tensile strength and elongation.The requirements for the mechanical properties of adhesives were fulfilled by the compositions containing 8.8% (w/w) of PE-PET and 20% (w/w) of PE-LW.     

Plasticized poly(3‐hydroxybutyrate) with improved melt processing and balanced properties

The widespread application of poly(3‐hydroxybutyrate) (PHB) in the food packaging and biomedical fields has been hindered by its high brittleness, slow crystallization, poor thermal stability, and narrow processing window. To overcome these limitations, a mixture of biodegradable and biocompatible plasticizers was used to modify PHB. Epoxidized soybean oil (ESO), acetyl tributyl citrate, poly(ethylene glycol) 4000 (PEG4000), and poly(ethylene glycol) 6000 (PEG6000) were tested to improve PHB melt processing and to achieve balanced thermal and mechanical properties. These plasticizers increased the flexibility and decreased the melt viscosity, improving the processability. The tensile strength was maintained within the limit of experimental error for ESO and decreased slightly (6–7%) for the other plasticizers. PEG6000 and ESO delayed the decomposition process of PHB. The plasticizers did not hinder the crystallization, and poly(ethylene glycol)s increased the crystallinity. The change in the interplanar distance and crystallite size, correlated with lamellar stack dimensions, gave more information on the plasticizers' effects in PHB. The blend with 5 wt % ESO was considered suitable for the fabrication of marketable PHB films. This study showed that it is possible to tailor the rheological, thermal, and mechanical behavior of a commercial PHB through the addition of a second plasticizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44810.     

Physical properties of water‐blown rigid polyurethane foams from vegetable oil‐based polyols

Fifty vegetable oil‐based polyols were characterized in terms of their hydroxyl number and their potential of replacing up to 50% of the petroleum‐based polyol in waterborne rigid polyurethane foam applications was evaluated. Polyurethane foams were prepared by reacting isocyanates with polyols containing 50% of vegetable oil‐based polyols and 50% of petroleum‐based polyol and their thermal conductivity, density, and compressive strength were determined. The vegetable oil‐based polyols included epoxidized soybean oil reacted with acetol, commercial soybean oil polyols (soyoils), polyols derived from epoxidized soybean oil and diglycerides, etc. Most of the foams made with polyols containing 50% of vegetable oil‐based polyols were inferior to foams made from 100% petroleum‐based polyol. However, foams made with polyols containing 50% hydroxy soybean oil, epoxidized soybean oil reacted with acetol, and oxidized epoxidized diglyceride of soybean oil not only had superior thermal conductivity, but also better density and compressive strength properties than had foams made from 100% petroleum polyol. Although the epoxidized soybean oil did not have any hydroxyl functional group to react with isocyanate, when used in 50 : 50 blend with the petroleum‐based polyol the resulting polyurethane foams had density versus compressive properties similar to polyurethane foams made from 100% petroleum‐based polyol. The density and compressive strength of foams were affected by the hydroxyl number of polyols, but the thermal conductivity of foams was not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

Low‐molecular‐weight glycerol esters as plasticizers for poly(vinyl chloride)

Phthalates are the most important plasticizers used in the polymer industry. However, their fossil origin and the results of recent tests showing their potential negative effect on human health have encouraged the polymer industry to turn toward non‐phthalate plasticizers. At the same time, the biodiesel industry produces a surplus of glycerol, thus leading the scientific community to seek new applications for this substance. This paper presents the performance of eight esters derived from glycerol as plasticizers for poly(vinyl chloride), including tests to evaluate their compatibility. Results show that glycerol esters obtained from propanoic, butanoic, isobutanoic, isopentanoic, and benzoic acids, while volatile, can be used as poly(vinyl chloride) plasticizers in certain applications. J. VINYL ADDIT. TECHNOL., 20:65–71, 2014. © 2014 Society of Plastics Engineers