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.     

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.     

Thermal and mechanical properties of electron beam irradiated poly(vinyl chloride)/polystyrene blends

The effect of electron beam irradiation on the thermal and mechanical properties of poly(vinyl chloride)/polystyrene (PVC/PS) blends and PVC/PS blends containing epoxidized natural rubber (ENR) was studied. The thermogravimetric analysis study showed that the thermal decomposition of the plasticized PVC individual polymer goes through two stages, whereas PS decomposes through one stage. However, the temperature of the maximum rate of reaction (T_max) of PS is much higher than that for PVC and their blends. Meanwhile, the T_max was found to increase with increasing PS ratios in the blend. The thermal stability of PVC/PS blends was greatly increased after electron beam irradiation in comparison with unirradiated blends. Moreover, the addition of ENR to PVC/PS increased the thermal stability. On the other hand, the mechanical properties in terms of tensile strength and elongation at break of PVC/PS blends are lower than pure PVC polymer because of the immiscibility. However, the addition of ENR to the PVC/PS (80/20) blend increased the elongation at break from 114 to 321% associated with a small effect on the tensile properties. These behaviors were supported by structure morphology studies observations, which indicate an improvement in the interfacial adhesion between the phases. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Properties of poly(vinyl chloride) incorporated with a novel soybean oil based secondary plasticizer containing a flame retardant group

A novel bio‐based plasticizer containing flame retardant groups based on soybean oil (SOPE) was synthesized from epoxidized soybean oil (ESO) and diethyl phosphate through a ring‐opening reaction. PVC blends plasticized with ESO and SOPE were prepared, respectively. Properties including rheological behavior, thermal stability, flame retardant performance, mechanical properties of PVC plasticized with ESO and SOPE were carefully studied. The results showed that the plasticized PVC blends indicated better compatibility, thermal, and mechanical properties. As a novel bio‐based plasticizer containing flame retardant groups, the TGA data indicated that the thermal degradation temperature of PVC blends plasticized with SOPE could reach to 275.5°C. LOI tests and SEM indicated that the LOI value of PVC blends could increase from 24.2 to 33.6%, the flame retardant performance of SOPE was put into effect by promoting polymer carbonization and forming a consolidated and thick flame retardant coating quickly, which is effective to prohibit the heat flux and air incursion. The enhancement in flame retardancy will expand the application range of PVC materials plasticized with SOPE. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42111.     

Plasticization of PVC with ethylene copolymer resins

Ethylene copolymer resin (ECR) modifiers, designed to be soluble in all proportions in PVC, form a wide variety of plasticized PVC blends. These solid, high molecular weight (Mw > 250,000) resin modifiers, unlike conventional liquid plasticizer, exhibit outstanding permanence in PVC. Compounding procedures, used for liquid plasticized PVC, are sometimes inadequate to produce homogeneous blends of PVC/ECR. A number of effective melt compounding techniques and a new family of ECR modifiers have been developed to produce homogeneous blends exhibiting many outstanding properties, including fluids/chemical resistance, high/low-temperature service, and weatherability.     

Preparation and properties of water‐swellable elastomer

A series of water‐swellable elastomers were prepared by blending chlorinated polyethylene (CPE) with poly(acrylic acid–acrylic amide) [P(AA–AM)]. The effect of component on its water‐absorbent properties such as degree of swelling, swelling ratio, and weight loss ratio was discussed. Mechanical behavior of blends was also investigated. The results indicate that swelling rate of CPE/P(AA–AM) was very quick; the blend reached its equilibrium state in only 30 min. The equilibrium swelling ratio increased with increasing amounts of water‐absorbent resin, the greater the amount of P(AA–AM), the higher the swelling degree. The effect of temperature on swelling ratio was very interesting, below 30°C, with an increase of temperature, the swelling ratio of blend increased, but above 30°C, with an increase of temperature, the swelling ratio decreased, indicating that this is a temperature‐sensitive water‐swellable elastomer. The effect of pH of solutions on the swelling behavior showed that water absorption of blends was heavily influenced by pH. The effect of different metal ions on the swelling behavior were also studied and the results showed that the absorption of blends was decreased dramatically with increasing the charge number of the cation, but was not influenced by radius and valence state of the anion. Owing to the compatibility of the amphiphilic graft copolymer (CPE‐g‐PEG), the equilibrium swelling ratio of the blends increased and the weight loss ratio decreased. Adding CPE‐g‐PEG can improve the mechanical behavior of blends. But too much grafted copolymer can worsen the tensile strength of blends. Tensile strength of blends decreased with an increase in P(AA‐AM). After absorbing water, the material's strength is greater than in the dry state. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1719–1723, 2004     

Compatibilization of poly(vinyl chloride) and polystyrene blends with poly(styrene‐co‐n‐methylolacrylamide)

In this work, the compatibilization of blends of plasticized polyvinyl chloride (PVC) and polystyrene (PS) with poly(styrene‐co‐n‐methylolacrylamide) (PSnMA) was investigated. The PSnMA was synthesized by emulsion polymerization with different amounts of n‐methylolacrylamide (nMA). Particle size and phase behavior was determined by scanning electron microscopy, and mechanical properties were determined in an Universal Testing Machine. Micrographs revealed that an appreciable size reduction of the dispersed phase was achieved when small amounts of PSnMA were added to the blend, and as the amount of nMA was increased, particle size decreased. When the (PVC/PS/PSnMA) blend was subjected to solvent extraction to remove PS and unreacted PVC, the residue showed a single T_g. Tensile modulus and the ultimate strength of the blends increased with PSnMA content. © 2008 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     

PAAS含量对吸水膨胀型PVO／OMTPV性能的影响

采用交联聚丙烯酸钠（PAAS）为吸水材料,通过动态硫化法制备了聚氯乙烯（PVC）j氯化聚乙烯橡胶（cM）热塑性硫化胶（TPV）,并对其力学性能、微观相态结构及吸水行为进行了研究。结果表明：在实验范围内,PVC／PAAS／CMTPV呈现出典型弹性体软而韧的应力应变行为;PAAS在基体中实现了均匀分散,且随着PAAS含量的增加,PVC／PAAS／CMTPV的力学性能呈下降趋势;PVC／PAAS／CMTPV的吸水性能随着PAAs的含量增加而显著提高,且在PAAS加入量为60phr时急剧增加;由于基体的屏蔽作用,PVC／PAAS／CMTPV没有出现明显的溶出现象。     

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.     

BA悬浮溶胀接枝聚合PVC的制备与性能研究

采用水相悬浮溶胀聚合的方法在PVC颗粒内部原位接枝丙烯酸丁酯(BA),考察了反应温度、分散剂用量对接枝反应和颗粒形态的影响,结果表明:接枝率随反应温度的升高而增大,分散剂用量为1.0份时,产物的颗粒形态规则,与PVC共混物的力学性能较好.PVC-g-BA/PVC共混体系动态力学性能分析(DMA)的结果表明:两相呈微观相态分离的结构特点;转矩流变性能测试结果表明:交联剂用量为3份时,PVC-g-BA/PVC共混体系的塑化性能较好.     

Influence of interfacial interactions on the properties of PVC/cellulosic fiber composites

The surface properties at the interface between thermoplastic and cellulosic fibers strongly influence the mechanical properties of plastic/cellulosic fiber composites. This paper examines the role of surface acid-base properties of plasticized PVC and cellulosic fibers on the mechanical properties of the composites. The acid-base surface characteristics of cellulosic fibers were modified by treating the fibers with γ-aminopropyltriethoxysilane (A-1100), dichlorodiethylsilane, phthalic anhydride, and maleated polypropylene. The empirical acid (K_A) and base (K_D) characteristics (i.e., electron donor/acceptor abilities) of untreated and treated fibers, as well as plasticized PVC, were determined using inverse gas chromatography (IGC) technique. These parameters were used to yield information on the acid-base pair interactions that were correlated with the tensile and notched Izod impact properties of the composites. Acid-base pair interactions have been found to be a valuable parameter in the design of surface modification strategies intended to optimize the tensile strength of the composites. By tailoring the acid-base characteristics of cellulosic fibers and plasticized PVC, a composite with equal tensile strength and greater modulus than unfilled PVC was developed. However, the acid-base factors did not correlate with tensile modulus, the elongation at break, and the notched Izod impact property of PVC/newsprint fiber composites. Aminosilane has been observed to be a suitable adhesion promoter for PVC/wood composites improving significantly the tensile strength of the composites. Other treatments (dichlorodiethylsilane, phtalic anhydride, and maleated polypropylene) were found to be ineffective, giving similar strength compared to the composites with untreated cellulosic fibers. FTIR spectroscopy results suggested that aminosilane was effective because treated cellulosic fibers can react with PVC to form chemical bonds. The resulting bond between PVC and cellulosic fibers accounts for the effectiveness of aminosilane, when compared with other coupling agents.     

Plastification of poly(vinyl chloride) by polymer blending

Blends of poly(vinyl chloride) (PVC) with different copolymers have been studied to obtain a plasticized PVC with improved properties and the absence of plasticizer migration. The copolymers used as plasticizers in the blends were acrylonitrile butadiene rubber, ethylene vinyl acetate (EVA), and ethylene-acrylic copolymer (E-Acry). Blends were studied with regard to their processing, miscibility, and mechanical properties, as a function of blend and copolymer composition. The results obtained were compared with those of equivalent compositions in the PVC/dioctyl phthalate (DOP) system. Better results than PVC/DOP were obtained for PVC/acrylonitrile butadiene rubber blends. The plasticizing effect on PVC of EVA and E-Acry copolymers was similar to that of DOP. It is shown that crosslinking PVC/E-Acry blends or increasing the vinyl acetate content in PVC/EVA blends, are alternatives that can increase the compatibility and mechanical properties of these blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1303–1312, 2000     

Dynamic mechanical and morphological studies on the compatibility of plasticized PVC/thermoplastic polyurethane blends

In this work, the compatibility of blends of plasticized poly(vinyl chloride) (p‐PVC) and thermoplastic polyurethane (TPU) was investigated using a dynamic mechanical analyzer and scanning electron microscopy. Two kinds of TPU with different ratios of hard to soft segments, i.e., TPU90 and TPU70 were compared. p‐PVC/TPU90 and p‐PVC/TPU70 blends with variable weight ratios (100/0, 90/10, 80/20, 70/30, 60/40, 50/50, 0/100) were prepared by melt blending. PVC was plasticized with 40 phr of dioctyl phthalate. It was found that TPU with a lower hard segment (i.e., TPU70) is more compatible with plasticized PVC than TPU with a higher hard segment (i.e., TPU90) in over the composition ranges examined. It was concluded that the compatibility of plasticized PVC and TPU are dependent on the ratio of hard to soft segments in TPU. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 415–422, 1999     

Polyblends. I. Mechanical properties of polyblends of butadiene–acrylonitrile elastomers and copolymers of vinyl stearate and vinyl chloride

Several nitrile rubber elastomers were polyblended, across the composition range, with selected polymeric compositions containing vinyl chloride. The compositions incorporated were (a) bulk poly(vinyl chloride) (PVC); (b) copolymers of vinyl stearate and vinyl chloride containing, respectively, 0.21, 0.36, and 0.47 weight fraction of the vinyl ester; and (c) mixtures containing the same weight fractions of di-2-ethylhexyl phthalate (DOP) with PVC. Mechanical, viscoelastic, optical, and volatility properties were studied on all blends in this first paper. To accurately compare the mechanical properties of polyblends of different systems, a criterion of mechanical equivalence was taken as the observance of similar stresses at break for compositions selected to have identical 100% moduli. Optimum mechanical equivalence, therefore, occurred at the largest ratios of 100% modulus to break stress for all systems compared. Optimum mechanical property equivalence was observed for NBR blends with PVC and for similar blends of both internally and externally plasticized systems containing 0.21 weight fraction of plasticizer. However, considerably more nitrile rubber was needed for PVC blends to acquire the properties of the plasticized systems. Mechanical equivalence was observed, but was not optimum for systems having more plasticizer because tensile strengths were lower. Polyblending with NBR improved the toughness and low-temperature properties of starting vinyl stearate copolymers. Improved toughness was indicated by the expansion of areas under stress–strain curves. Refractive index matching appeared to explain the transparency of the best films and their relative freedom from haze. On heating at 85°C, poly(vinyl chloride) and the copolymer polyblends suffered no volatility loss. Volatility of DOP from the blends was 1.5 times greater than for PVC–DOP mixtures. Because modulus–temperature curves and mechanical T_g values of the filler component shifted with composition, the mechanical behavior of these blends was in harmony with an accepted standard of interdomain compatibility.     

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     

吸水膨胀型软质聚氯乙烯/羧甲基纤维素共混物的研究

采用扫描电子显微镜等仪器测试并研究了聚氯乙烯(PVC)/羧甲基纤维素(CMC)共混物的结构与性能。结果表明:随着吸水树脂含量的增加,共混物的吸水率和体积膨胀率增大,拉伸强度和断裂伸长率降低;随着水浸泡时间的增加,拉伸强度和断裂伸长率降低;吸水后PVC/CMC共混物中CMC分散相粒径明显增大,与基体树脂界面相互作用下降。     

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     

软质PVC／NBR共混材料改善电冰箱门封的低温弹性

研究了丁腈橡胶（ＮＢＲ）弹性体对软质聚氯乙烯低温弹性及力学性能的影响,并探讨了该共混竽电冰箱门封的加工工艺性及其优点。     

防水用吸水膨胀橡胶的研制

采用物理共混法制取天然橡胶 /交联聚丙烯酸钠共混物吸水膨胀性橡胶 (WSR)。考察了该共混体系的硫化特性及增容剂、吸水树脂用量、硫磺用量等对WSR吸水性能的影响。结果表明该体系的硫化速度比普通橡胶快 ,加入增容剂可大大提高WSR的吸水速率及最大吸水率 ,且能显著改善试样的外观质量。当天然橡胶 /聚丙烯酸钠质量比为10 0 /10 0时 ,增容体系吸水率最高达到 1832 % (即原质量的 18倍左右 ) ,明显高于未增容体系 ,后者最高吸水率为14 31%