Plasticizers derived from cardanol: synthesis and plasticization properties for polyvinyl chloride(PVC)

Two natural plasticizers derived from cardanol (CD), cardanol acetate (CA) and epoxidized cardanol acetate (ECA), were synthesized and characterized by ¹H NMR and ¹³C NMR. The plasticizing effects of the obtained plasticizers on semi-rigid polyvinylchloride (PVC) formulations were also investigated. Two commercial phthalate ester plasticizers, dioctyl terephthalate (DOTP) and diisononyl phthalate (DINP), were used as controls. Mechanical and thermal properties, compatibility, thermal stability, microstructure, and workability were assessed by dynamic mechanical analysis (DMA), mechanical analysis, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and dynamic stability analysis, respectively. Results indicated that the natural plasticizer ECA had overallsuperior flexibility, compatibility, thermal stability, and workability comparable to both controls. The obtained CA and ECA have lower volatility resistance and similar extraction and exudation resistance than that of DOTP and DINP. The CA was further blended with DOTP in soft PVC films. Results of DMA, TGA and mechanicalanalysis indicated that CA can serve as a secondary plasticizer to improve the related properties of soft PVC formulations. These CD derived plasticizers show promise as an alternative to fully or partially replace petroleum-based plasticizers.     

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     

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.     

三醋酸甘油酯增塑聚乳酸共混体系热力学及动态力学性质

用三醋酸甘油酯(TA c)增塑聚乳酸(PLA),研究了TA c对PLA力学性能的影响。当塑化剂添加到15%之后抗张强度从64M Pa下降到29.9M Pa,断裂伸长率同时从5.6%升高到243.1%,可以达到吹膜所要求的性质。用DSC和DM A研究了该共混体系的相容性,观察到随着TA c含量的增大,线性降低了PLA的Tg和Tm,并且塑化剂提高了分子链的迁移性,也使得体系的结晶度增大。在塑化剂含量为25%时,PLA已经被塑化剂所饱和,继续添加塑化剂可能会导致两相分离。     

Effect of ketal group in castor oil acid-based plasticizer on the properties of poly(vinyl chloride)

Two castor oil acid esters containing a ketal or ketone group (KCL or CL), as alternative plasticizers for poly(vinyl chloride) (PVC), were prepared. The structures were confirmed by ¹H NMR and FTIR spectroscopies. The effects of the presence of a ketal or ketone group in these compounds on PVC plasticization were examined. The DMA and SEM results showed that both plasticizers were miscible with PVC and exhibited excellent plasticizing properties, compared to those of dioctyl phthalate (DOP). The PVC plasticized by KCL displayed a lower T_g value of 20.6 ° C, which was lower than that of PVC plasticized with DOP (22.3 ° C) and PVC plasticized with CL (40.5 ° C). Tensile tests indicated that PVC plasticized using KCL showed a 37% higher of elongation at break than PVC plasticized by CL and 30% higher than PVC plasticized by DOP. The plasticizing mechanism was also investigated. Moreover, exudation, volatility, and extraction tests, along with TGA indicated that the presence of ketal groups effectively improved the migration resistance of plasticizer and the thermal stability of PVC blends. Taken together, introducing ketal groups into plasticizer might be an effective strategy for improving its plasticizing efficiency.     

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.     

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     

分子模拟技术应用于增塑PVC结构与性能研究

应用特定的分子模拟计算技术,研究了3种增塑剂邻苯二甲酸二辛酯(DOP)、癸二酸二辛酯(DOS)、偏苯三酸三辛酯(TOTM)对聚氯乙烯(PVC)在增塑剂吸收速度、力学性能、硬度和相对电容率等方面的影响.结果表明:分子模拟微观图可在一定程度上解释不同增塑剂在PVC力学及相对电容率等方面性能的差异,并能解释随DOP用量增加,材料力学性能变化的原因.     

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.     

The effects of plasticizers on the dynamic mechanical and thermal properties of poly(lactic acid)

Poly(lactic acid) (PLA) was blended with five plasticizers in a batchwise mixer and pressed into films. The films were analyzed by means of dynamic mechanical analysis and differential scanning calorimetry to investigate the properties of the blends. Triacetine and tributyl citrate proved to be effective as plasticizers when blended with PLA. The glass transition temperature of PLA decreased linearly as the plasticizer content was increased. Both plasticizers were miscible with PLA to an extent of ～ 25 wt %. At this point, the PLA seemed to be saturated with plasticizer and the blends tended to phase separate when more plasticizer was added. There were also signs of phase separation occurring in samples heated at 35, 50, and 80°C, most likely because of the material undergoing crystallization. The presence of the plasticizers induced an increased crystallinity by enhancing the molecular mobility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1227–1234, 2002     

Oligomeric isosorbide esters as alternative renewable resource plasticizers for PVC

Oligo(isosorbide adipate) (OSA), oligo(isosorbide suberate) (OSS), and isosorbide dihexanoate (SDH) were synthesized and evaluated as renewable resource alternatives to traditional phthalate plasticizers. The structure of the synthesized oligomers was confirmed by nuclear magnetic resonance spectroscopy (¹H‐ and ¹³C‐NMR), and molecular weight was determined by size exclusion chromatograph. The plasticizers were blended with poly(vinyl chloride) (PVC), and the miscibility and properties of the blends were evaluated by differential scanning calorimetry, fourier transform infrared spectroscopy, tensile testing, and thermogravimetry. Especially the blends plasticized with SDH had almost identical properties with PVC/diisooctyl phthalate (DIOP) blends. The blends containing OSA and OSS plasticizers, based on dicarboxylic acids, had somewhat lower strain at break but higher stress at break and better thermal stability compared to the PVC/DIOP or PVC/SDH blends. All the synthesized isosorbide plasticizers showed potential as alternative PVC plasticizers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Palm oil‐based compound as environmentally friendly plasticizer for poly(vinyl chloride)

Many plasticizers have been invented to serve the purpose of making poly(vinyl chloride) (PVC) into a more flexible plastic. In this work, the potential of palm oil‐based compound (Palm1) as a polymeric plasticizer for PVC was investigated. Plasticization of PVC was conducted via the solvent casting technique, using tetrahydrofuran (THF) as the mutual solvent. Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC) were used to find evidence of interactions between the plasticizer and PVC. Transition temperatures (T_gs) of the plasticized PVC were obtained using DSC, and their thermal stabilities were evaluated using a thermogravimetric analyzer (TGA). Results from the study show that the polymeric plasticizer could interact with PVC chains via polar interaction involving –C‐Cl of PVC and possibly the ‐OH groups of Palm1. T_g of the PVC was reduced after it was plasticized with Palm1. The results obtained from this study suggest that the Palm1 may have the potential to serve as an environmentally friendly plasticizer for PVC. J. VINYL ADDIT. TECHNOL., 22:80–87, 2016. © 2014 Society of Plastics Engineers     

An innovative plasticizer for sensitive applications

Di(isononyl) cyclohexane‐1,2‐dicarboxylate (HEXAMOLL® DINCH) is a new plasticizer for PVC. In the tests used, it has no indication of toxicity or genotoxicity; it is biodegradable; and it has low sensitizing properties. Its properties in PVC compare favorably to those of other plasticizers having well‐balanced properties. This plasticizer should be well‐suited for sensitive applications.     

Effect of Wood Flour Content on the Thermal,Mechanical and Dielectric Properties of Poly(vinyl chloride)

Several composite formulations of poly(vinyl chloride)/olive wood flour (PVC/WF) were manufactured by dry‐blending PVC, wood flour, plasticizer and other processing additives in a high‐intensity mixer. The dry‐blended compounds were calendered into film samples (T = 180°C, calendered time = 8 min). The films obtained are cut into normalized samples for thermal, mechanical, and dielectric characterization. The results obtained show that stress as well as strain at break decrease sharply as the wood flour content increases. On the other hand, this filler content has little influence on the glass transition temperature. It decreases the temperature of decomposition setting and retards the PVC thermal decomposition. It increases permittivity as well as dielectric losses. The thermal stability, as measured by thermogravimetry (TGA) and differential scanning calorimetry (DSC) methods, is good enough to permit processing of these types of PVC compounds using conventional processing techniques and temperatures under 210°C.     

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

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

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

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

Transparency of rubber‐toughened polymer blend containing plasticizer

Transparency and its temperature dependence were studied for rubber‐toughened polymer blends composed of poly(methyl methacrylate), core–shell latex–rubber particles, and plasticizers such as tricresyl phosphate and di(2‐ethylhexyl)adipate. The transparency of the blends was found to be improved by the addition of the plasticizers. This phenomenon is attributed to the uneven distribution of the plasticizer in the blends. Furthermore, it was found that the plasticizers improve the transparency in a wide temperature range, because the plasticizer addition reduces the difference in the thermal expansion, and thus the temperature dependence of the refractive index, between poly(methyl methacrylate) and the rubber phases. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40775.     

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.     

Thermal and surface characterization of plasticized starch polyvinyl alcohol blends crosslinked with epichlorohydrin

Starch‐polyvinyl alcohol (PVA) blends in 2:8 wt % were prepared with various plasticizers such as polyethylene glycol (PEG‐200, PEG‐400) and glycerol. The crosslinking of starch‐PVA blends by epichlorohydrin was carried out in the presence of a plasticizer in situ. The obtained films were analyzed by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), dynamic mechanical and thermal analysis (DMTA), and X‐ray photoelectron spectroscopy (XPS), and remarkable changes in thermal stability and glass‐transition temperature have been observed on plasticizing and crosslinking in different concentrations. Different kinetic models such as Coats–Redfern, Broido, Friedman, and Chang were used to calculate the kinetic parameters of thermal decomposition. The results suggest that the thermal stability and activation energy of thermal decomposition passes through maxima at a critical concentration of plasticizer and increases with increasing crosslinker concentration. High‐resolution C 1s XPS analysis was used to provide a method of differentiating the presence of various carbons associated with different environment in the films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 25–34, 2006