A new biobased plasticizer for poly(vinyl chloride) based on epoxidized cottonseed oil

The use of epoxidized cottonseed oil as plasticizer for poly(vinyl chloride) was studied. The plasticizer content was set to 70 phr and the optimum isothermal curing conditions were studied in the temperature range comprised between 160 and 220 °C with varying curing times in the 7.5–17.5 min range. The influence of the curing conditions on overall performance of cured plastisols was followed by the evolution of mechanical properties (tensile tests with measurements of tensile strength, elongation at break, and modulus), change in color, surface changes of fractured samples by scanning electron microscopy (SEM), thermal transitions by differential scanning calorimetry, and migration in n‐hexane. The optimum mechanical features of cured plastisols are obtained for curing temperatures in the 190–220 °C range. For these curing conditions, fractography analysis by SEM gives evidences of full curing process as no PVC particles and free plasticizer can be found. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43642.     

Meaningful evaluation of plastisol gelation and fusion temperatures by dynamic mechanical analysis

In most PVC plastisol processing operations, gelation and fusion characteristics of the plastisol are critically important. For example, in chemically foamed plastisols, plastisol fusion temperature and blowing agent decomposition temperature must be carefully coordinated. In rotomolded parts, rates of gelation may determine the quality of the finished parts. For plastisol products made by any process, the final fusion temperature determines the processing temperatures required to give the finished product acceptable mechanical properties. For a variety of reasons, the methods commonly used to characterize plastisol gelation and fusion (hot bar test, resin in plasticizer clear point, torque rheometer measurements, etc.) provide comparisons between plastisols but do not provide temperatures that are easily related to actual industrial processes. With dynamic mechanical analysis (DMA), one can characterize, under low shear conditions, the temperatures at which gelation begins, gelation ends, and complete fusion occurs. Additionally, it is possible to record plastisol viscosities (and other dynamic mechanical properties) over the processing temperature range. We used a multiple linear regression program to analyze the DMA data for plastisols heated from 30 to 210°C and containing either 70, 80 or 90 phr of Jayflex dihexyl phthalate (DHP) or Jaylflex di-isodecyl phthalate (DIDP). Further, we determined the plasticizer phr dependence and the reproducibility of gel and fusion temperatures given by data analyzed in this manner. Finally, for comparison, we analyzed the reproducibility of initial and final plastisol gel temperatures and fusion temperatures, which were determined by visually analyzing the DMA data for plastisols containing 70, 80, and 90 phr of Jyflex plasticizers DHP, Jayflex 77, diisononyl phthalate (DINP), and DIDP. Precise characterization of plastisol gelation and fusion behavior will, undoubtedly, facilitate substitution of plastisol ingredients as is often required by those who manufacture and process plastisols.     

Studies of electrical and mechanical properties of poly(vinyl chloride) mixed with electrically conductive additives

Different samples of poly(vinyl chloride) (PVC) compositions were formulated from PVC, a polar plasticizer such as dioctylphthalate (DOP), and variable proportions of electrically conductive additives such as fast extrusion furnace (FEF) carbon black (CB), poly(vinylpyridine) (PVP), or polyacrylonitrile (PAN). Epoxidized soybean oil was added as a heat stabilizer. Samples of the PVC–CB system were also prepared by dispersing different concentrations of CB into the PVC matrix. The electrical studies showed that the addition of CB to the PVC–DOP system produces a plasticized PVC with high electrical conductivity whereas the compounding of PVC with CB produces a sample with much higher electrical conductivity. The effect of the structure of PVP and PAN on the electrical and mechanical properties of the PVC–DOP system was also studied to obtain a semiconductive plasticized PVC with good mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1590–1598, 2004     

DSC study of foamable poly (vinyl chloride‐co‐vinyl acetate) plastisols of different commercial plasticizers

In this article the characterization of the thermal behavior of foamable PVC (Poly (vinyl chloride)) plastisols from 20 different plasticizers has been studied by differential scanning calorimetry (DSC). The interactions between the resin and the plasticizer as well as the decomposition of the azodicarbonamide (ADC)—the chemical blowing agent (CBA) used—have been analyzed. The latter process is of crucial importance for the knowledge of plasticized PVC flexible foam formation. Clear effects of the chemical nature of the plasticizers and their molecular weight (M_w) have been observed, both in the interactions (swelling and early stages of gelation) between the resin and the plasticizer, as well as in the temperature of the ADC decomposition and the shape of the DSC peak. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Determination of gelation temperature of poly(vinyl chloride) by thermomechanical and thermogravimetric parameters

Preheating between the temperatures of 200 and 280°C is done to a film‐structured poly(vinyl chloride) (PVC) sample, which has a gelation temperature ∼ 250°C. After this preheat, the PVC's thermomechanical and thermal differences, at temperatures before and after thermal gelation, are observed. Consequently, when some thermomechanical and thermal parameters, obtained at temperatures before and after gelation, are compared, it can be said that this is an easier method to determine the gelation temperature of a polymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1635–1640, 2005     

Rheology,morphology, and mechanical and thermal properties of recycled PVC pipes

This article demonstrated the possibility of recycling PVC pipes by investigating the effect of adding PVC pipes (varying from 0 to 80 % wt) into two commercial PVC virgin grades on the rheological, morphological, mechanical, and thermal properties of the PVC blends. The results obtained showed an increase in the melt viscosity and no change in the die swell ratio as the concentration of the recycled PVC was increased. The die swell ratio was observed to increase with temperature, this being associated with the presence of gelation that occurred at high temperature. The optimum tensile and impact strengths were detected, the impact strength being explained by use of SEM micrographs of the fracture surface. The hardness result corresponded well to the density of the compounds. The glass transition, degradation, and heat-deflection temperatures were also found to shift with the recycled PVC loading. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2478–2486, 2001     

Soft PVC foams: Study of the gelation,fusion, and foaming processes. I. Phthalate ester plasticizers

The use of foamed plastics gains more and more interest every day. Flexible poly(vinyl chloride) (PVC) foams have excellent mechanical properties and low price, thus their application is extensive. Foams are produced from plastisols, which are based on the suspension of the PVC resin in a plasticizer. Phthalates are the most used plasticizers in flexible PVC foam formation. In this study, we have studied the influence of the phthalate ester‐type plasticizers on the foaming process and the quality of the foams obtained from the corresponding plastisols. For the plastisols prepared with the nine phthalate plasticizers considered, we have studied and discussed the complex and extensional viscosities; the thermal behavior (DSC) including the decomposition of the chemical blowing agent, and the foam production by rotational molding. In addition, we have characterized the foams obtained by thermomechanical analysis, density, and bubble size distribution. As expected, clear correlations have been obtained between the molecular weight and structure of the plasticizer with the rheological behavior of the plastisols. The knowledge of the gelation and fusion processes and evolution of the extensional viscosity of the plastisols combined with the study of the thermal decomposition of the blowing agent in each plastisol allows for better understanding of the complex dynamic behavior of these foaming systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Kinetic analysis of the thermal degradation of PVC plastisols

The thermal degradation of plasticized polyvinyl chloride (plastisol) is reported here. Plastisols used in the present work were prepared with the plasticizer diethylhexyl phthalate in different proportions. Thermogravimetric analysis has been applied to study the behavior of plastisols at high temperatures and to evaluate their degradation kinetics. Several tests were carried out at different heating rates and the variation of the degree of reaction with time and temperature was calculated. The influence of the heating rate in dynamic measurements (5–40°C/min) on kinetic parameters, such as activation energies and reaction orders, has also been studied. These parameters were calculated from dynamic thermogravimetric analysis tests using Friedman analysis and a kinetic model for the degradation of poly(vinyl chloride) and plastisols has been then developed. The obtained model was able to simulate the thermal degradation process of plastisols in dynamic conditions and was used to evaluate the effects of additives in the degradation. The results of this study can be used to optimize the concentration of plasticizers and stabilizers in poly(vinyl chloride) formulations. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1069–1079, 1999     

Fusion behavior of plastisols of PVC studied by ATR-FTIR

The behavior of PVC plastisols during gelation and fusion was studied by the ATR-FTIR technique (Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy). DBP, DOP, and DIDP, three common phthalate plasticizers for PVC, were used in plastisols formulations. Three heating rates—5, 10 and 15°C/min—and formulations with different plasticizer concentrations were studied. The IR spectra of a plastisol coincides with the IR spectra of the plasticizer except for the bands at 1435 and 613 cm^?1 from the PVC (CH₂ wagging and C—Cl stretching, respectively). When the plastisol is heated, a progressive decrease of the plasticizer bands areas can be observed, while bands from PVC increase their intensity, probably because of the adsorption of the plasticizer by the resin. On cooling, the area of all bands follows the same path as when heating, but the paths separate at a certain temperature, showing the irreversible nature of this process. The analysis of the band at 1280 cm^?1 (C(O)—O from plasticizer) during heating and cooling, shows that the temperature of separation areas (T_s) takes place at temperatures coherent with plasticizer compatibility. Studies at different heating rates and different plasticizer content are in good agreement with results using other techniques, available in the literature.     

Viscoelasticity and mechanical properties of reactive PVC plastisols

Reactive poly(vinyl chloride) (PVC) plastisols have been developed to substitute the hydrocarbon diluents generally used in low viscosity PVC plastisols. For this purpose, methacrylate monomers (5–15%) were added in the PVC suspension (based on diisononyl phtalate plasticizer) to reduce the viscosity at room temperature and to polymerize (by radical polymerization initiated by an organic peroxide) during the gelation process. Both the reactive processing and the gelation process were carried out between the plates of a rheometer cell in the linear viscoelasticity domain (small deformation) and under increasing temperature from room temperature up to 160°C (ω = 6.283 rad s^?1, = 5°C min^?1). A temperature criterion was proposed to define the right balance between the polymerization and the gelation to get the best mechanical properties (i.e., elongation and stress at break). The polymerization process must be slower than the gelation process as the polymerization must take place when PVC grains have fused together to form a homogeneous medium at least at the microscale. Actually, the polymerization kinetics can be controlled by the decomposition kinetics of the organic peroxide. Finally, triethylene glycol dimethacrylate and lauryl methacrylate monomers and dicumyl peroxide as initiator turned out to be the best reactive system for some potential industrial applications. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Formulation and mechanical characterization of PVC plastisols based on low‐toxicity additives

New formulations of plastisols based on low‐toxicity plasticizers were proposed and characterized. Traditional phthalate plasticizers were replaced in the plastisols studied in this research by polymeric plasticizers (i.e., saturated polyesters), produced by the reaction of a diol and a carboxylic acid. The main drawback for the use of these plasticizers in formulations of PVC plastisols is a significant increase of the paste viscosity, which decreases their processability; thus, the use of additional additives to reduce viscosity is recommended. This study also includes the optimization of the processing conditions (cure temperature and time) of the proposed plastisols: complete cure was obtained at 140°C and 10 min. It is reported that the final properties of plastisols are very sensitive with respect to the processing conditions; in fact, insufficient plasticization or degradation can affect the material when processed out of the optimum conditions. The influence of the plasticizer concentration on mechanical and optical properties, such as tensile strength, hardness, brightness, and the like, is also reported. In summary, the proposed plastisols, with low‐toxicity plasticizers, offer a valid alternative to traditional PVC plastisols based on phthalate plasticizers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1881–1890, 2001     

Epoxidized Mesua ferrea L. seed oil‐plasticized thermostable PVC and PVC‐clay nanocomposites

The use of vegetable‐oil‐based polymeric plasticizers with nanotechnology can create new applications for plasticized poly(vinyl chloride) (PVC). Epoxidized Mesua ferrea L. (Ceylon Ironwood) seed oil was used as a plasticizer for PVC. Further, nanocomposites were prepared through an ex‐situ technique using epoxidized‐oil‐swelled organically modified montmorillonite (5 wt%) and PVC. Notable improvement in thermal and processing characteristics of the nanocomposites was observed over those of the virgin polymer (in both unplasticized and plasticized PVC), as studied by TGA. The prepared nanocomposites were characterized by FTIR, SEM, TEM, and XRD techniques. A dramatic decrease in viscosity (7‐fold) was observed in THF for a 10% solution of epoxidized‐oil‐modified PVC compared to unplasticized PVC in THF, as measured by Brookfield viscometer. Isothermal analysis at three different temperatures (100, 150, and 200°C) reveals sufficient stability of the epoxidized oil modified PVC nanocomposites, as confirmed by gravimetric and FTIR analysis. Augmentation of thermostability and good retention of mechanical properties of the (Mesua ferrea L.)‐plasticized‐PVC/clay nanocomposites with respect to rigid PVC vouch for the utility of the former as advanced industrial materials. J. VINYL ADDIT. TECHNOL., 18:168–177, 2012. © 2012 Society of Plastics Engineers     

Thermal and mechanical properties of silane-crosslinked poly(vinylchloride)

A comparative study has been made of the crosslinking of plasticized PVC by grafting of γ-aminopropyltriethoxysilane (ASi) and sodium γ-mercaptopropyltrimethoxysilane (NaMSi) during processing. The influence of type of reagent and concentration, and the rheological behavior were investigated to obtain a crosslinked material with improved mechanical properties and good thermal stability. Depending on the reagent concentration, different gel contents, ranging from 0–100%, were obtained with both reagents. For all crosslinked systems the mechanical properties above T_g were improved. In the case of ASi-crosslinked PVC, the thermal stability deteriorated significantly but, for NaMSi-crosslinked PVC, thermal stability remains close to that of raw PVC, and the separation of the grafting and crosslinking processes is more viable in this case. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 865–872, 1998     

无毒环保型增塑剂对聚氯乙烯性能的影响

选用了邻苯增塑剂(DOP)、柠檬酸酯类增塑剂（ATBC、ATOC）、对苯增塑剂（DOTP）、偏苯增塑剂（TOTM）及新型植物基增塑剂ID-37制备了增塑PVC材料,对所制备的PVC材料的拉伸强度、断裂伸长率、硬度、180℃热稳定性进行表征,测试结果表明,180℃静态热稳定性DOTP与TOTM最优,DOP与ID37次之,ATBC与ATOC相当。增塑剂对力学性能影响较小,对硬度差异影响较大,其中DOTP与TOTM所增塑PVC材料硬度比其余四种高约5度（邵氏A）。DSC测试结果表明,TOTM及ATBC增塑PVC的Tg相对较高,约为-22℃,其余四种较为接近,约为-25℃。     

Studies of electrical and mechanical properties of semiconductive poly(vinyl chloride) compositions

A sample of poly(vinyl chloride) (PVC) and a polar plasticizer consisting of dioctylphthalate (DOP) and triisopropylphenylphosphate (TIPPP) was prepared and found to possess some electrical conductivity. Different samples of PVC compositions were formulated from the PVC-DOP-TIPPP system and also variable proportions of the conductive materials polyaniline or the Ni salt of ethylene glycol bisadipate ester. Dibutyltindilaurate as a heat stabilizer, titanium oxide as a filler, and sandorin red 20 pigment were added. The effect of the structure of polyaniline and Ni adipate ester on the electrical and mechanical properties of the PVC–DOP–TIPPP system was studied to obtain a semiconductive plasticized PVC with good mechanical properties. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 685–693, 1998     

Mechanical and thermomechanical characterization of PVC/polyalkylacrylate blends

The effect of blending poly(ethyl acrylate) and poly(butyl acrylate) in various proportions with suitably stabilized and plasticized polyvinyl chloride (PVC) was studied with reference to their physical, mechanical, thermal, and morphological properties. The tensile modulus and ultimate tensile strength indicated a rise initially, followed by their steady decrease with increasing concentration of the polyalkyl acrylates. A corresponding behavior of elongation at break and toughness are exhibited. The various polyblends exhibit thermal stability over unmodified PVC, as reflected from their thermomechanical studies, in which the penetration is also inversely related to the respective moduli. The biphasic cocontinuous systems as explicit from the morphological studies support phase mixing at the initial stages, with subsequent phasing‐out tendency, with increasing percentage of polyalkyl acrylate incorporation. The thermomechanical parameters are in conformity to their mechanical parameters, which have been further supported by their morphological studies. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3698–3703, 2006     

Plasticizer factors influencing take-up by PVC resins

The ease with which plasticizer is combined with poly(vinyl chloride) resin is a measure of processing characteristics critical in the dry blending of suspension PVC and the gelation of plastisols. By using commercial grade plasticizers, this study developed predictive equations for the following processing parameters of dialkyl phthalates in PVC:

• Relative dry-blend rates in suspension PVC as a function of plasticizer viscosity.
• Relative initial gelation temperatures in plastisols as a function of plasticizer molecular weight and solvating strength.
• Relative final gelation temperatures in plastisols as a function of plasticizer solvating strength.

This information allows one to predict the relative processing characteristics of any dialkyl phthalate plasticizer for PVC on the basis of its chemical and physical properties.     

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.     

Effect of mechanochemical degradation on gelation and mechanical properties of PVC

The effect of vibromilling or jet milling on gelation and mechanical properties of poly(vinyl chloride) (PVC) was studied through SEM, FTIR, DSC, and mechanical properties tests. The experimental results show that the size of the grain and apparent density of PVC are decreased. The grains become much more loosely aggregated and the crystallinity of PVC is decreased during milling. The extensional fracture of degraded PVC is obviously different from that of undegraded PVC, the tensile strength and degree of gelation of degraded PVC are increased as compared with undegraded PVC. The mechanical properties of PVC are improved quite a lot after blending it with a small amount of mechanochemically degraded PVC. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2273–2281, 1997     

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.