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     

Synthesis of a novel polyester plasticizer based on glyceryl monooleate and its application in poly(vinyl chloride)

The use of bio‐based polymeric plasticizers could expand the application range of plasticized poly(vinyl chloride) (PVC) materials. In this study, a novel bio‐based polyester plasticizer, poly(glutaric acid‐glyceryl monooleate) (PGAGMO), was synthesized from glutaric acid and glyceryl monooleate via a direct esterification and polycondensation route. The polyester plasticizer was characterized by gel permeation chromatography, ¹H‐nuclear magnetic resonance, and Fourier‐transform infrared spectroscopy. The plasticizing effect of PGAGMO on PVC was investigated. The melting behavior, thermal properties, and mechanical properties of PVC blends were studied. The results showed that the PGAGMO could improve the thermal stability and reduce the glass transition temperature of PVC blends; when phthalates were substituted by PGAGMO in PVC blends, the thermal degradation temperature of PVC blends increased from 251.1°C to 262.7°C, the glass transaction temperature decreased from 49.1°C to 40.2°C, the plasticized PVC blends demonstrated good compatibility, and the decrement of the torque and the melt viscosity of PVC blends were conducive to processing. All results demonstrated that the PGAGMO could partially substitute for phthalates as a potential plasticizer of PVC. J. VINYL ADDIT. TECHNOL., 22:514–519, 2016. © 2015 Society of Plastics Engineers     

Epoxidized linolenic acid salts as multifunctional additives for the thermal stability of plasticized PVC

Calcium and zinc salts of epoxidized linolenic acid were synthesized and used as multifunctional additives, to minimize or prevent the reaction of epoxidized soybean oil (ESO) with liberated hydrochloric acid (HCl) during the thermal degradation of poly(vinyl chloride) (PVC) in particular. These metal epoxy salts were incorporated as thermal stabilizers for both diisodecyl phthalate and ESO–plasticized PVC blends that underwent thermal degradation studies at 170°C. The overall performance of these metal epoxy salts was examined by thermal gravimetric analysis and visual color retention of the PVC blends. The weight loss profiles of the metal salt stabilized PVC were comparable to those of blends containing metal stearates. There were, however, vast improvements in color retention of the plasticized PVC using these novel additives. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41736.     

The effect of an epoxidized plasticizer on the thermo-oxidative ageing of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers

The effects of an epoxidized plasticizer on the mechanical properties and thermo-oxidative ageing behaviour of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers (TPEs) were investigated. Aged and unaged blends were characterized by FTIR, tensile properties, tear strength, hardness and dynamic mechanical analysis (DMA). The properties of the epoxidized soya oil (ESO) plasticized TPEs were compared with those of the di-2-ethylhexylphthalate (DOP) plasticized counterparts. The presence of epoxide groups in ESO has been shown to produce two conflicting effects. On the one hand, the presence of excessive epoxide groups has resulted in poor ageing behaviour. On the other hand, it has resulted in a good interaction and compatibility with PVC/ENR. It was found that the tensile strength of the ESO plasticized blends were comparable with the DOP plasticized ones, but the elongation at break (EB) of the ESO blends fell short of that of the DOP blends. Also the retention of both tensile properties for the ESO blends was poorer than for DOP blends. Hardening and embrittlement also occurred in the ESO blends. Despite these weaknesses, ESO could be an ideal plasticizer for the PVC/ENR system as indicated by plasticizer permanence and the greater efficiency of plasticization. © 1998 SCI.     

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     

Synthesis and application of a novel cardanol‐based plasticizer as secondary or main plasticizer for poly(vinyl chloride)

A novel plasticizer based on cardanol, hydrogenated cardanol glycidyl ether acetic ester containing phosphaphenanthrene group (HCGEP), was prepared and incorporated into poly(vinyl chloride) (PVC) for the first time. The molecular structure was characterized with Fourier transform infrared and ¹H NMR spectroscopies. The thermal degradation behavior and flame retardant performance of PVC films with HCGEP as secondary or main plasticizer were investigated using thermogravimetric analysis, combustion tests, limiting oxygen index tests and morphological analysis of residues. Furthermore, the mechanical properties of PVC films were examined based on the results of tensile testing. The results were compared to those of the petroleum‐based plasticizer dioctyl phthalate. With the substitution of dioctyl phthalate with HCGEP, PVC films exhibited high thermal stability and better flame retardant performance. The tensile test results showed that the addition of HCGEP could endow PVC resin with well‐balanced properties of flexibility, strength and hardness. © 2017 Society of Chemical Industry     

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.     

Synthesis and properties of boron-containing soybean oil based thermosetting copolymers

The first example of boron-containing soybean oil based copolymers was prepared from soybean oil, styrene, divinylbenzene and 4-vinylphenyl boronic acid by cationic polymerization using boron trifluoride etherate as initiator. Soxhlet extraction and NMR spectroscopy indicate that the copolymers consist of a crosslinked network plasticized with varying amounts of oligomers and unreacted oil. The thermal degradation mechanism was studied and the thermal, dynamomechanical and flame retardant properties of these materials were examined. Thermosets with glass transition temperatures ranging from 43 to 60 °C, which are thermally stable below 350 °C and with LOI values from 23.7 to 25.6 were obtained. The LOI tests indicate that the flame retardant properties of vegetable oil can be improved by adding boron covalently bonded to the polymer.     

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.     

Blends of triazine‐based hyperbranched polyether with LDPE and plasticized PVC

Triazine‐based hyperbranched polyether was obtained by earlier reported method and blended with low density polyethylene (LDPE) and plasticized poly(vinyl chloride) (PVC) separately to improve some desirable properties of those linear polymers. The properties like processability, mechanical properties, flammability, etc. of those linear polymers were studied by blending with 1–7.5 phr of hyperbranched polyether. The mechanical properties were also measured after thermal aging and leaching in different chemical media. SEM study indicates that both polymers exhibit homogenous morphology at all dose levels. The mechanical properties like tensile strength, elongation at break, hardness, etc. of LDPE and PVC increase with the increase of dose level of hyperbranched polyether. The flame retardant behavior as measured by limiting oxygen index (LOI) for all blends indicates an enhanced LOI value compared to the polymer without hyperbranched polyether. The processing behavior of both types of blends as measured by solution viscosity and melt flow rate value indicates that hyperbranched polyether acts as a process aid for those base polymers. The effect of leaching and heat aging of these linear polymers on the mechanical properties showed that hyperbranched polyether is a superior antidegradant compared to the commercially used N‐isopropyl‐N‐phenyl p‐phenylene diamine. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 648–654, 2007     

Effect of hydrated fillers and red phosphorus on the limiting oxygen index of poly(ethylene‐co‐vinyl actate)‐poly(vinyl butyral) and low density polyethylene‐poly(ethylene‐co‐vinyl alcohol) blends

The limiting oxygen index (LOI) values of EVA‐PVB and low density polyethylene (LDPE)‐poly(ethylene‐co‐vinyl alcohol) (EVOH) polymer blends containing hydrated filler‐type flame retardants and red phosphorus were measured. When used as the sole flame retardant, magnesium hydroxide [Mg(OH)₂] and alumina trihydrate (ATH) performed best in EVA and PVB, respectively. Magnesium hydroxide addition had a limited effect on the LOI of plasticized PVB, and addition of red phosphorus made little difference. This result is attributed to a mismatch between the decomposition temperature of Mg(OH)₂ and the temperature at which the PVB plasticizer vaporizes. Otherwise, low‐level addition of red phosphorus significantly improved LOI values. The presence of hydroxyl groups on the polymer backbone had a beneficial effect with respect to LOI values in ATH‐filled blends. An LOI value of 30 was achieved in EVOH with as little as 32% of ATH and 3% of red phosphorus. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers     

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.     

Evaluation of the effects of acetyl tributyl citrate as bio‐based plasticizer on the physical,thermal, and dynamical mechanical properties of poly(vinyl chloride)/polymethyl methacrylate blends

This article details our work in studying the plasticization of Poly(vinyl chloride) (PVC)/Polymethyl methacrylate (PMMA) blends with bio‐based acetyl tributyl citrate (ATBC) in place of conventional plasticizers such as di(2‐ethylhexyl) phthalate. PMMA was blended with PVC in various ratios from 0 to 100 wt% by melt compounding with or without the plasticizer ATBC. Both the glass transition temperatures of the blends (differential scanning calorimetry) and Tα (dynamic mechanical thermal analysis) are consistent with a miscibility of the components, and Fourier transforms infrared spectroscopy studies show that there are specific interactions in the PVC/PMMA blends favoring the miscibility. The thermal degradation of the blends was studied by thermogravimetric analysis that shows the thermal degradation of rigid and plasticized PVC/PMMA is a process composed of two‐steps and that PMMA exercises a stabilizing effect on the thermal degradation of PVC during the first step by decreasing the rate of dehydrochlorination. J. VINYL ADDIT. TECHNOL., 25:E73–E82, 2019. © 2018 Society of Plastics Engineers     

Preparation of aluminum hydroxide/aluminum phosphinate flame‐retardant poly(vinyl alcohol) foam through thermal processing

A novel flame‐retardant poly (vinyl alcohol) (PVA) composite foam was prepared successfully through thermal processing, which was filled with high content of flame retardant, based on aluminum hydroxide (ATH) and aluminum phosphinate (AlPi) and using water as plasticizer and blowing agent. The flame‐retardant property and mechanism of the prepared foam matrix were studied by vertical burning test, limiting oxygen index (LOI), cone calorimeter, scanning electronic microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The experimental results showed that the PVA/ATH/AlPi (1/1.2/0.05) composite achieved LOI value of 41% and UL94 V‐0 (3.2 mm) rate. The addition of ATH and AlPi into PVA matrix significantly decreased flammability of the composites, because a more compact and continuous char layer of the PVA/ATH/AlPi composite could be formed, due to the involvement of AlPi in the char‐forming reaction. Compared with the pure PVA sample, the peak heat release rate (PHRR) and total heat release (THR) of PVA/ATH/AlPi (1/1.2/0.05) composite were reduced by 76.5% and 58.2%, respectively. Built upon this PVA‐based foam matrix with good flame retardancy, the flame‐retardant PVA‐based foam was successfully prepared through thermal extrusion. In addition, the influence of water content on melt viscosity, foam structure and mechanical strength was also analyzed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42020.     

The mechanical properties and thermal performances of polypropylene with a novel intumescent flame retardant

A novel intumescent flame retardant: tetra‐spirophosphoryl‐benzoguanamine (TSPB) containing three constituents was used as a new flame retardant for polypropylene to prepare flame‐retardant materials, whose flammability and thermal behavior were studied by the limited oxygen index (LOI), thermogravimetric analysis (TGA), in addition whose mechanical properties were investigated in this work. It was found that when the addition of TSPB was 25 wt %, the LOI value of the PP could achieve to 29.5 and pass the UL‐94 V‐0 rating test. The TGA data showed that TSPB could enhance the thermal stability of PP and effectively increase the char residue formation. The mechanical performance test showed that the addition of TSPB improve the mechanical performances of PP to some extent. Thus, the trinity intumescent flame retardant TSPB is good to modify PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

一种新型蓖麻油酸季戊四醇酯的制备及应用

用季戊四醇和蓖麻油酸通过酯化反应反应制备了蓖麻油季戊四醇酯。采用红外光谱仪和核磁共振仪对制备的产品的化学结构进行表征。并将其作为增塑剂与聚氯乙烯（PVC）共混,研究了塑化PVC的平衡扭矩、热性能和力学性能,对该增塑剂在不同溶媒中的耐迁移性进行了研究,并与邻苯二甲酸二辛酯和环氧大豆油的塑化性能进行了对比。结果表明,蓖麻油季戊四醇酯塑化PVC的加工平衡扭矩为14.9 N·m,改善了PVC的加工稳定性;塑化PVC的拉伸强度为23.28 MPa,断裂伸长率为263.13 %,耐迁移性能较邻苯二甲酸酯和环氧豆油较好,可以作为PVC增塑剂使用。     

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.     

Migration of additives from food grade polyvinyl chloride (PVC) films: Effect of plasticization by polymeric modifiers instead of conventional plasticizers

Based on the static and dynamic mechanical properties of the corresponding blends, the compatibility of six thermoplastic elastomers with polyvinyl chloride (PVC) was investigated. A terpolymer of ethylene, vinyl acetate and carbon monoxide (EVACO) was shown to give the optimal properties for the processing of transparent, soft, PVC‐based films. FTIR spectroscopic analysis of EVACO plasticized blends clearly shows that the interactions involve the carbonyl groups of the VA and not of the CO monomer units. The migration phenomenon was studied on PVC based samples plasticized with di‐2‐ethylhexyladipate (DEHA) and EVACO in varying amounts. The overall migration (OM) was monitored by the weight loss percentage of the samples immersed into isooctane at 40°C. The specific migrations of DEHA (SM_D) and epoxidized soybean oil (SM_E) were shown to be responsible for the overall migration (OM = SM_D + SM_E). The weight percentages of DEHA and epoxidized soybean oil (ESO) were correlated to the excess of immersion temperature (40°C) over the varying glass transition temperature of the samples. The results are explained with respect to the plasticizing effect of the additives and to the permanency of the EVACO‐plasticization.. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1291–1299, 2003