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.     

Application of Poly(butylenes 2-methylsuccinate) as Migration Resistant Plasticizer for Poly(vinyl chloride)

The bio-based and biodegradable polyester poly(butylenes 2-methylsuccinate) (PBM) was successfully used as a polymeric plasticizer to modify poly(vinyl chloride) (PVC) in this work. The tensile properties, plasticization efficiency estimated by the lowered glass transition temperature and the enhanced elongation at break of the PVC/PBM blends and the migration stability of the PBM were investigated. It was indicated that the migration-resistant property of PVC plasticized with PBM was greatly superior to that with dioctyl phthalate (DOP). Furthermore, the tensile properties were comparable to that of PVC/DOP, indicating that the environmentally friendly PBM can be used as an alternative plasticizer to remove the potential health risks from migrating phthalates during applications.     

Poly(hexane succinate) plasticizer designed for poly(vinyl chloride) with a high efficiency,nontoxicity, and improved migration resistance

Poly(hexane succinate) (PHS) was designed as an alternative type of polyester plasticizer for the modification of poly(vinyl chloride) (PVC). The plasticizing effect of PHS was studied and compared with the traditional dioctyl phthalate (DOP) plasticizer. The results show that the PVC plasticized by PHS had the lowest tensile strength of 15.3 MPa and the highest elongation at break of 105.1% when 35 phr PHS was added. It also exhibited a lower glass‐transition temperature than PVC plasticized by DOP (PVC–DOP); this could be explained by the improvement of free volume for the amorphous part of PVC enhanced by high‐molecular‐weight PHS. The migration‐resistant properties of PVC–PHS was greatly superior to those of PVC–DOP. All of these results illustrate that PHS had a higher plasticizing efficiency than DOP for PVC. PHS could be used as an alternative plasticizer to remove the potential health risks of phthalates migrating out during applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46388.     

Viscoelastic properties,morphology, and thermal stability of rigid and plasticized poly(vinyl chloride)/poly(methyl methacrylate) blends

Viscoelastic properties, morphology, and thermal stability of rigid and plasticized poly(vinyl chloride)/poly (methyl methacrylate) (PVC/PMMA) blends were studied. For that purpose, blends of variable composition from 0 to 100 wt% were prepared in the presence (15, 30, and 50 wt%) and in the absence of di(2‐ethylhexyl) phthalate as plasticizer. Their miscibility was investigated by using dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The DMTA and SEM results showed that the two polymers are miscible. Thermogravimetric studies on these blends were carried out in a flowing atmosphere of air from ambient temperature to 550°C. The results showed that the thermal degradation of rigid and plasticized PVC/PMMA in this broad range of temperature is a three‐step process and that PMMA exerted a stabilizing effect on the thermal degradation of PVC during the first step by reducing the rate of dehydrochlorination. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Isothermal and Dynamic Thermogravimetric Degradation of Rigid and Plasticized Poly(Vinyl Chloride)/Poly(Methyl Methacrylate) Blends

The thermal degradation of rigid and plasticized poly(vinyl chloride) (PVC)/poly (methyl methacrylate) (PMMA) blends was investigated by means of isothermal and dynamic thermogravimetric analysis in a flowing atmosphere of air. For that purpose, blends of variable composition from 0 to 100 wt% were prepared in the presence (15, 30 and 50 wt%) and in the absence of di-(2-ethyl hexyl) phthalate (DEHP) as plasticizer. The thermal degradation of the blends was investigated by isothermal thermogravimetry at 180°C during 120 min. It was found that the main processes are the dehydrochlorination of PVC and depolymerization of PMMA. The dynamic thermogravimetric experiments were carried out in the temperature range of 30 ? 550°C. The results showed that the thermal degradation of rigid and plasticized PVC/PMMA blends in this broad range of temperatures is a three-step process and that PMMA exerted a stabilizing effect on the thermal degradation of PVC during the first step by reducing the dehydrochlorination.     

Sustainable synthesis of bio‐based hyperbranched ester and its application for preparing soft polyvinyl chloride materials

In this study, bio‐based hyperbranched ester was synthesized from castor oil. The chemical structure of the bio‐based hyperbranched ester obtained was characterized with Fourier transform infrared and ¹H NMR spectra. Soft polyvinyl chloride (PVC) materials were prepared via thermoplastic blending at 160 °C using bio‐based hyperbranched ester as plasticizer. The performances including the thermal stability, glass transition temperature (T_g), crystallinity, tensile properties, solvent extraction resistance and volatility resistance of soft PVC materials incorporating bio‐based hyperbranched ester were investigated and compared with the traditional plasticizer dioctyl phthalate (DOP). The results showed that bio‐based hyperbranched ester enhanced the thermal stability of the PVC materials. The T_g of PVC incorporating bio‐based hyperbranched ester was 23 °C, lower than that of PVC/DOP materials at 28 °C. Bio‐based hyperbranched ester showed a better plasticizing effect, solvent extraction resistance and volatility resistance than DOP. The plasticizing mechanism is also discussed. © 2018 Society of Chemical Industry     

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.     

Stabilization of epoxidized soybean oil‐plasticized poly(vinyl chloride) blends via thermal curing with genistein

In an effort to alleviate the well‐known toxicity effect of phthalate derivatives on human health, genistein (G) modified epoxidized soybean oil (ESBO) has been investigated as an alternative “green” plasticizer for poly(vinyl chloride) (PVC) with potential application in medical products. As evidenced by a single glass transition that shifts systematically with composition in conjunction with the melting point depression of G crystals, ESBO is not only a good plasticizer to PVC, but also miscible with G. Moreover, ESBO is an excellent compatibilizer to the immiscible PVC/G pair. Furthermore, PVC/ESBO/G ternary blends revealed complete miscibility in the amorphous state. Of particular interest is that ESBO‐plasticized PVC is thermally curable with G at elevated temperatures above 220 °C and affords relatively stable G modified ESBO‐plasticized PVC for blood contact medical applications such as blood bags and hemodialysis tubings. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46472.     

Influence of crystallinity in the curing mechanism of PVC plastisols

The influence of the crystalline areas observed in poly(vinyl chloride) (PVC) the mechanical and thermal properties of PVC plastisols was studied. Several industrial‐degree PVC resins were used to obtain a broad range of molecular weights and processing conditions for PVC plastisols. The gelation process was fully studied at different temperatures and was related to the existence of crystalline areas at high temperatures, even near the glass transition. A simple explanation of the phenomena observed during the gelation of plasticized PVC is proposed, according to the variation in the mechanical and thermal properties at different temperatures. The final gelation was obtained at 140–150°C, which was a lower temperature than those at the beginning of the thermal degradation process. The thermodynamic aspects of the gelation of plasticized PVC were mainly controlled by the PVC resin properties, whereas the plasticizer only influenced the diffusion and stability of the material. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 538–544, 2004     

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     

聚癸二酸甘油单月桂酸酯的合成及对聚氯乙烯增塑性能的研究

以甘油单月桂酸酯和癸二酸为原料,以钛酸正丁酯为催化剂,在180℃下合成了高分子量聚酯产品：聚癸二酸甘油单月桂酸酯。采用红外光谱、核磁共振仪和凝胶渗透色谱仪对豆油聚酯的结构和分子量进行了表征;并将该聚酯作为增塑剂与聚氯乙烯热塑共混成型后,采用热重分析仪、差示扫描量热仪和万能拉力试验机对共混物的热性能和力学性能进行了表征。结果显示：通过甘油单月桂酸和癸二酸的直接缩聚反应得到了高分子量聚癸二酸甘油单月桂酸酯,该聚酯产品能够提高聚氯乙烯的热稳定性,降低聚氯乙烯的玻璃化转变温度,可以与邻苯类增塑剂复配,得到热性能与力学性能兼顾的聚氯乙烯产品。     

Thermal stability and Kinetic Study of rigid and plasticized Poly(vinyl chloride)/Poly(methylmethacrylate) blends

The thermal stability and kinetic parameters for degradation of rigid and plasticized poly(vinyl chloride)/poly (methylmethacrylate) blends have been investigated by using nonisothermal thermogravimetry in a flowing atmosphere of air. For that purpose, blends of variable composition from 0 to 100 wt% were prepared in the presence (15, 30, and 50 wt%) and in the absence of di‐(‐2‐ethyl hexyl) phthalate as plasticizer. Measurements were carried out in the temperature range of 30–550°C and at various heating rates (5, 10, 20, and 40°C/min). The kinetic parameters (E_a and A) were determined by applying the integral Kissinger method. Results indicate that these parameters and the thermal stability of the blends are dependent on the blend composition and the amount of plasticizer present. J. VINYL ADDIT. TECHNOL., 21:102–110, 2015. © 2014 Society of Plastics Engineers     

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     

聚1,2-丙二醇新戊二醇己二酸酯增塑性能的研究

将合成的聚1,2-丙二醇新戊二醇己二酸酯(简称PG-AA-NPG)聚酯增塑剂增塑PVC的试片制成复合材料,并进行耐迁移、DSC、力学性能、热稳定性能测试,分析PG-AA-NPG的综合性能,并且与加入DOP和市售聚酯增塑剂A的PVC试片进行对比.结果表明PG-AA-NPG的耐溶剂迁移性优于DOP;PVC/PG-AA-NP...     

Poly(vinyl chloride) films plasticized with novel poly‐nadic‐anhydride polyester plasticizers

In this work, several novel poly‐nadic‐anhydride polyester plasticizers were developed to be used in poly(vinyl chloride) (PVC) film fabrication for the first time. Mechanical properties of the films, the compatibility of plasticizers in PVC resin, as well as testing of migration of the plasticizers, were performed in order to evaluate the efficiency of plasticization. Scanning electron microscopy, Fourier‐transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry were used to characterize the unplasticized and plasticized polymer. The results demonstrated that the as‐prepared poly‐nadic‐anhydride plasticized PVC film significantly improved the plasticization efficiency of PVC film based on the increase in the break in elongation of the films. According to scanning electron microscopy analysis, the poly‐nadic‐anhydride polyester plasticizers presented good compatibility with PVC resin. In volatility and extraction tests, PVC films plasticized with the poly‐nadic‐anhydrides showed enhanced migration resistance. The plasticizing effects induced by the poly‐nadic‐anhydride polyester plasticizers were also confirmed by a glass transition temperature shift toward lower temperatures in the plasticized films. J. VINYL ADDIT. TECHNOL., 23:321–328, 2017. © 2015 Society of Plastics Engineers     

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.     

Synthesis and application of a novel thermostable epoxy plasticizer based on levulinic acid for poly(vinyl chloride)

Epoxy bisphenol acid isooctyl ester (EBAIE) was synthesized and characterized by FTIR and H-NMR. EBAIE was used as poly(vinyl chloride) (PVC) plasticizer for the first time, and its addition amount was 30 wt% of PVC. The mechanical properties, thermal stability, compatibility, and decomposition activation energy of PVC blends were systematically studied. Compared to the commercial plasticizer-dioctyl phthalate (DOP), the tensile strength had been significantly increased from 30.64 to 45.07 MPa, while the elongation at break had little difference. The thermal stability analysis showed that the static stability time at 180°C had been extended from 40 to 300 min. The decomposition activation energy indicated that the EBAIE plasticized PVC was with a higher thermal stability. The extraction and volatility resistance of the novel plasticizer were superior to those of DOP.     

Poly(lactic acid) plasticized by biodegradable glyceryl lactate

The esterification of glycerol with lactic acid was carried out to synthesize glyceryl lactate, which was used as a as a plasticizer with different contents and blended with poly(lactic acid) (PLA) to get a completely biodegradable material with potential applications because of its biodegradability. The structural, morphological, thermal, and mechanical properties of the plasticized PLA were studied to evaluate the plasticizing effects. The results show that the PLA plasticized with glyceryl lactate had a lower glass‐transition temperature and a better ductility. With increasing plasticizer content, the crystallinity of PLA increased. The elongation at break reached 380%, and the impact strength was 1.7 times that of neat PLA. Simultaneously, the migration rate measurements showed that glyceryl lactate presented relatively low migration toward the surface compared with glycerol and citrate esters. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43460.     

Synthesis and application of a natural plasticizer based on cardanol for poly(vinyl chloride)

A natural plasticizer with multifunctional groups, similar in structure to phthalates, cardanol derivatives glycidyl ether (CGE) was synthesized from cardanol by a two‐step modification process and characterized by FT‐IR, ¹HNMR, and ¹³CNMR. The resulting product was incorporated to PVC (CGE/PVC), and plasticizing effect was compared with PVC incorporated with two kinds of commercial phthalate ester plasticizers bis (2‐ethylhexyl) benzene‐1,4‐dicarboxylate (DOTP) and diisononyl phthalate (DINP). Dynamic mechanical analysis and mechanical properties testing of the plasticized PVC samples were performed in order to evaluate their flexibility, compatibility, and plasticizing efficiency. SEM was employed to produce fractured surface morphology. Thermogravimetric analysis and discoloration tests were used to characterize the thermal stabilities. Dynamic stability analysis was used to test the processability of formulations. Compared with DOTP and DINP plasticized samples, CGE/PVC has a maximum decrease of 9.27% in glass transition temperature (T_g), a maximum increase of 17.6% in the elongation at break, and a maximum increase of 31.59°C and 25.31 min in 50% weight loss (T50) and dynamic stability time, respectively. The obtained CGE also has slightly lower volatility resistance and higher exudation resistance than that of DOTP and DINP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42465.