Effect of electron‐beam irradiation on poly(vinyl chloride)/epoxidized natural rubber blend: dynamic mechanical analysis

The irradiation‐induced crosslinking in 50/50 poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend was investigated by means of dynamic mechanical analysis. The influence of trimethylolpropane triacrylate on the irradiation‐induced crosslinking of PVC/ENR blends was also studied. The enhancement in storage modulus and T_g with irradiation dose indicated the formation of irradiation‐induced crosslinks. This is further supported by the decrease in tan δ_max and loss modulus peak. The compatibility of the blend was found to be improved upon irradiation. The Fox model was used to provide a further insight into the irradiation‐induced compatibility in the blend. Scanning electron microscopy studies on the cryofracture surface morphology of the blends as well as the homopolymer have been undertaken in order to gain more evidence on the irradiation‐induced crosslinking. © 2001 Society of Chemical Industry     

Electron‐beam irradiation of poly(vinyl chloride)/epoxidized natural rubber blends in presence of trimethylolpropane triacrylate

Electron‐beam initiated crosslinking of poly(vinyl chloride)/epoxidized natural rubber blends, which contained trimethylolpropane triacrylate (TMPTA), was carried out over a range of irradiation doses (20–200 kGy) and concentrations of TMPTA (1–5 phr). The gel content increased with the irradiation dose and the TMPTA level, although the increase was marginal at higher doses and higher TMPTA levels. Blends containing 3–4 phr TMPTA achieved optimum crosslinking, which in effect caused the maximum tensile strength (TS) at a dose of 70 kGy. A further addition of TMPTA caused a decline in the TS above 40 kGy that was due to embrittlement, which is a consequence of excessive crosslinking and the breakdown of the network structure. The possible formation of a more open network as a result of the breakdown of the network structure was further confirmed by the modulus results. Dynamic mechanical analysis (tan δ curve) and scanning electron microscopy studies on samples irradiated at 0 and 200 kGy were undertaken in order to gain further evidence on the irradiation‐induced crosslinking. The plasticizing effect of TMPTA prior to irradiation and the formation of microgels upon irradiation were also discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1926–1935, 2001     

Contact angle behaviour of poly(vinyl chloride)/ epoxidized natural rubber miscible blends

—Contact angle studies of miscible poly(vinyl chloride)/epoxidized natural rubber (PVC/ ENR) blends were carried out in air using water and methylene iodide. The solid surface free energy was calculated from harmonic mean equations. Blending of PVC and ENR decreased their contact angle or increased their solid surface free energy due to the improved chain mobility, and the accumulation of excess polar sites at the surface through conformational alterations resulting from the specific interaction of PVC and ENR. The work of adhesion, interfacial free energy, spreading coefficient, and Girifalco-Good's interaction parameter changed markedly with the blend composition. In blends, PVC and ENR improved hydrophilicity, and wettability with polar and non-polar liquids. The presence of a plasticizer in PVC, in general, further improved the wettability and hydrophilicity in blends.     

Mechanical and thermo-oxidative properties of blends of poly(vinyl chloride) with epoxidized natural rubber and acrylonitrile butadiene rubber in the presence of an antioxidant and a base

Being polar and compatible with poly(vinyl chloride), epoxidized natural rubber (ENR) is similar in behaviour to acrylonitrile butadiene rubber (NBR). To assess the extent of this similarity, the mechanical properties of 50/50 blends of PVC with these two rubbers were compared. Their response to thermo-oxidative ageing in the presence of an antioxidant and a base was also investigated by ageing the blends at 100°C for 7 days. Studies involving mechanical properties and FTIR were used to evaluate the extent of thermal degradation. The results revealed that blends of ENR show mechanical properties which are as good as, and in some instances better than, those of the NBR blends. However, the ENR blends with PVC are very prone to oxidative ageing. This might be attributed to the susceptibility of the oxirane group to ring-opening reactions, particularly in the presence of PVC, which yields HCl as it degrades. The amine-type antioxidant 2,24-trimethyl-1,2-dihydroquinoline (TMQ) improved the oxidative stability of both blends. This was more significant in the ENR blend, which in some cases attained stability comparable with that of NBR. The addition of a base, calcium stearate [Ca(St)₂], did not show any influence in the PVC/ENR blend, even though it was expected to curb acid-catalysed degradation. Ca(St)₂, however, improved the oxidative stability of the PVC/NBR blend. The combination of optimum amounts of TMQ and Ca(St)₂ effectively improved the tensile strength of both unaged blends, without appreciable adverse effect on elongation at break. This combination also imparted stability better than that of TMQ alone.     

Oil-resistance studies of dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomer

Dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) thermoplastic elastomers (TPEs) were prepared with a Brabender plasticorder coupled with a mixing attachment by melt mixing. The blends were prepared at 150°C at a rotor speed of 50 rpm. Curatives concentration was steadily increased from 0 to 1 phr in order to study the vulcanization effect on the plasticized blend. The effectiveness of the dynamic vulcanization was indicated by the Brabender plastograms. The properties investigated include mass swell, tensile strength, elongation at break, modulus at 100% elongation (M100), tear strength, and hardness. The PVC/ENR samples were exposed to two types of environments, namely, air and oil under otherwise identical conditions. The effect of oil and thermooxidative aging on the mechanical properties were characterized at room temperature and 100°C. It was found that at ambient temperature the samples immersed in oil possessed similar properties to those that were exposed to air. Significant enhancement in mechanical properties were observed for both environments at 100°C. This has been attributed to the increase in crosslink density which was manifested by a steady reduction in percent mass swell with increased sulfur loading. The excellent mechanical behavior of the PVC/ENR TPEs even after immersing the samples in oil at 100°C has provided a good indication of the oil resistance of the materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1357–1366, 1998     

Developments of high performance vibration absorber from poly(vinyl chloride)/chlorinated polyethylene/epoxidized natural rubber blend

A high performance vibration absorber requires a high loss factor behavior over a wide temperature and frequency range. An investigation was carried out to prepare such materials based on poly(vinyl chloride), chlorinated polyethylene, and epoxidized natural rubber ternary blends. The loss factor and damping behavior of several compositions were measured using a viscoelastic spectrometer and a polymer‐laminated steel cantilever‐beam damping device. Suitable compositions were found to give good mechanical properties and high loss factor over a wide temperature and frequency range. It was also observed that flake‐type fillers improve the damping behavior. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 855–863, 1999     

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.     

The effect of epoxide content on compatibility of poly(lactic acid)/epoxidized natural rubber blends

The objective of this work was to determine the effect of the epoxide content in epoxidized natural rubber (ENR) on the miscibility and compatibility with poly(lactic acid) (PLA) in prepared PLA/ENR blends. PLA was blended with 10 wt% of ENRs (epoxidized at 10, 15, 20, and 25 mol%). The presented study showed that the in situ graft copolymer, PLA-g-ENR, was formed during melt blending in the blends containing 10 and 15 mol% ENR. This work is the initial study showing the presence of PLA-g-ENR in the blends by ¹H-NMR and ¹³C-NMR. PLA-g-ENR acted as a compatibilizer, producing a partially miscible blend, indicated by an inward shift of the α-transition temperatures of PLA and ENR in the blends. PLA-g-ENR also greatly reduced the particle size of ENR and increased the impact strength, tensile strength, and elongation at break of the blends. The epoxide content of ENR changed deformation mechanisms of the blends.     

Rheological and viscoelastic behavior of dynamically vulcanized poly(vinyl chloride)–epoxidized natural‐rubber thermoplastic elastomers

Dynamically vulcanized poly(vinyl chloride)–epoxidized natural‐rubber thermoplastic elastomers (PVC–ENR TPEs) were prepared using a semi‐EV vulcanization system. The compounds were melt‐mixed, and the rheological behavior was evaluated. The effect of curatives concentration on the rheological behavior using the shear dependence of viscosity and the activation energy for viscous flow was evaluated. Viscoelastic behavior was also investigated with the Monsanto MDR 2000. The parameters studied include the elastic modulus at maximum torque, the loss peak at maximum torque, and their ratio (tan δ). The data obtained were correlated with the material properties, such as hardness and resilience. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2886–2893, 1999     

Self‐crosslinking and cocrosslinking with nitrile rubber of poly(vinyl chloride) with pendent N,N‐diethyldithiocarbamate group

In order to realize the self‐crosslinking and cocrosslinking of poly(vinyl chloride) (PVC) with nitrile‐butadiene rubber (NBR), PVC with pendent N,N‐diethyldithiocarbamate groups (PVC‐SR) was prepared from the reaction of PVC with sodium SR in butanone. The PVC‐SR was self‐crosslinked and the PVC‐SR/NBR blend was cocrosslinked under heating at 170°C. The effect of the degree of functionality of PVC‐SR on the torque, gel content, glass‐transition temperature, and tensile properties was investigated. The results showed that the crosslinking reaction did not occur for PVC, NBR, or the PVC/NBR blend. Introducing the SR groups into PVC caused the crosslinking reaction to occur and the high gel contents of the crosslinked samples were obtained in 15 min. The degree of crosslinking increased with the degree of functionality of PVC‐SR. The mechanism of the crosslinking reaction was discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 634–638, 2001     

Peroxide crosslinking of rigid poly(vinyl chloride)

The optimum conditions for crosslinking rigid poly(vinyl chloride) with trimethylolpropane trimethacrylate (TMPTMA) and peroxide have been examined. The extent of crosslinking was measured by determining gel content by Soxhlet extraction in tetrahydrofuran. Mechanical properties were measured at 130°C and dynamic viscoelastic measurements were carried out to detect changes in the glass transition temperature (T_g). It was found that 15 phr of TMPTMA and 0.3 phr of peroxide were optimum concentrations for maximizing the extent of crosslinking, tensile strength, and T_g. The lower molding temperature of 170°C was preferred to minimize thermal degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2904–2909, 2007     

Radiation crosslinking of poly(vinyl chloride)/epoxidized natural rubber blend: effect of lead stabilization of the poly(vinyl chloride) phase

The irradiation crosslinking of 50/50 poly(vinyl chloride)/epoxidized natural rubber blend was investigated in the presence of 1–5 parts per hundred resin (phr) tribasic lead sulfate (TBLS) with blends prepared at various mixing temperatures. The blends were irradiated using a 3.0 MeV electron accelerator at 0, 100 and 200 kGy irradiation doses. Changes in tensile strength, elongation at break and stress‐strain curves of the blends with the increase TBLS content and blending temperatures were observed before and after irradiation. The results on the tensile properties revealed the inhibition of the irradiation‐induced crosslinking by the TBLS although it stabilizes the blend against thermal and irradiation‐induced degradation. The Fourier transform infrared spectroscopy studies further confirmed these observations. Control on the thermal degradation of the blend during blending found to be crucial in achieving maximum enhancement in blend properties upon irradiation. Evidence from dynamic mechanical analysis was also used to support this contention. Addition of 2 phr TBLS and blending at 150 °C found to be adequate in order to achieve the best enhancement in blend properties through irradiation‐induced crosslinking. © 2001 Society of Chemical Industry     

Peroxide crosslinking of unplasticized poly(vinyl chloride)

A crosslinking system consisting of 1,1‐di‐t‐butylperoxy‐3,3,5‐trimethyl cyclohexane peroxide and trimethylolpropane trimethacrylate (TMPTMA) has been used to introduce crosslinks into unplasticized poly(vinyl chloride) (PVC). The influence of the concentration of both reagents has been investigated, and crosslinking monitored by determination of the remaining sample weight after Soxhlet extraction with tetrahydrofuran. The system used (i.e., 0.5–2.0 phr peroxide with 5 to 15 phr TMPTMA) has been shown to be effective for crosslinking PVC. Gel contents of 30–40% have been obtained, premature crosslinking during processing is largely avoided, but thermal stability still needs to be improved. Considerable improvements in elevated temperature mechanical properties can be attained using an appropriate TMPTMA/peroxide concentration. The best tensile properties were obtained with 0.5 phr peroxide and 15 phr TMPTMA. Observed increases in T_g, also achievable with only 0.5 phr peroxide, but only slightly dependent on TMPTMA concentration, represent a useful increase in service temperature for the resulting compound. Lower peroxide levels may be adequate to achieve property improvements. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2657–2666, 2000     

丁腈橡胶/聚氯乙烯/受阻酚AO-60共混物的结构与性能

用差示扫描量热法、X射线衍射法、扫描电子显微镜及元素分析法分析了丁腈橡胶(NBR)/聚氯乙烯(PVC)/四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(AO-60)共混物的结构,并研究了共混物的阻尼性能及力学性能。结果表明,当AO-60用量小于50份时,其分子在基体中以非晶态形式存在;当AO-60用量超过50份时,过量的AO-60形成聚集体并在基体中形成少量的晶体;NBR/PVC/AO-60共混物内部呈现“海相-岛相”结构,连续相主要是NBR,而分散相主要是PVC与AO-60分子。NBR/PVC/AO-60共混物的损耗因子-温度曲线呈双峰特征,且随着AO-60用量的增加,峰值明显增大。当AO-60用量为50份时,NBR/PVC/AO-60共混物的综合力学性能较佳。     

Electron beam irradiation of epoxidized natural rubber: FTIR studies

The effect of irradiation on the structure of epoxidized (50 %) natural rubber (ENR50) has been studied using Fourier transform infrared spectroscopy (FTIR). ENR50 was irradiated using a 3.0 MeV electron beam machine with doses ranging from 20 to 200 kGy. The influence of several additives such as trimethylolpropane triacrylate (TMPTA). Irganox®1010, and tribasic lead sulfate on the irradiation‐induced changes of ENR50 is investigated. Upon irradiation, ring opening of epoxide groups, and oxidation and crosslinking of residual double bonds occurred, leading to decreases in the intensities of epoxide and cis double bond bands and an increases in ether, furan and hydroxyl bands. Gel fraction and hardness values have been used to correlate changes in the structure of the rubber upon irradiation. The results show that the increase in gel fraction upon irradiation of pure ENR50 can be associated with irradiation‐induced crosslinking, ring opening side‐chain reactions of oxirane groups and oxidation at the cis‐double bonds. The addition of Irganox®1010 and tribasic lead sulfate inhibits irradiation‐induced reactions in ENR50 to a considerable extent. The importance of TMPTA in preventing intramolecular ring opening side‐chain reactions is also discussed. However, our studies do not reveal the exact nature of the irradiation‐induced reactions involved in ENR. © 2000 Society of Chemical Industry     

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.     

环氧树脂增强聚氯乙烯/丁腈橡胶共混胶的性能

用环氧树脂(EP)增强聚氯乙烯/丁腈橡胶(PVC/NBR)共混胶,研究了EP用量对共混胶力学性能的影响,考察了EP对炭黑增强PVC/NBR共混胶力学性能的影响,并用扫描电子显微镜分析了共混胶的微观形貌。结果表明,用EP增强PVC/NBR共混胶,胶料的力学性能提高,且老化后性能变化不明显。在EP用量为18份左右时共混胶的综合性能最佳。EP对炭黑增强PVC/NBR共混胶力学性能的改善有一定作用。EP在PVC/NBR共混胶中原位聚合生成了直径约为200 nm的纤维。     

Compatibilization of poly(lactic acid)/epoxidized natural rubber blend with maleic anhydride

The objective of this work was to determine the compatibilization effect of different concentrations of maleic anhydride (MA) in poly(lactic acid) blended with epoxidized natural rubber (PLA/ENR). ENR-grafted MA [ENR-g-MA] was synthesized using four concentrations of MA: 0.15, 0.30, 0.45, and 0.60 phr. Using an internal mixer, binary (PLA/ENR, PLA/ENR-g-MA) and ternary (PLA/ENR/ENR-g-MA) polymer blends were prepared with a constant rubber content of 10 wt %. ENR impaired the mechanical properties of PLA, perhaps due to the relatively large size of the rubber particles. The compatibilization effect of MA was evaluated from the results of impact strength testing. ENR-g-MA was a toughening agent for PLA when the concentration of MA was in the range of 0.30–0.60 phr. MA increased miscibility between PLA and ENR. This effect was indicated in the blends by reductions in rubber particle size, the glass transition temperature of PLA, and the α-transition temperatures of PLA and ENR. In the binary polymer blends, the MA concentration in ENR-g-MA that produced the optimal mechanical properties of PLA was 0.60 phr. In the ternary blends, mechanical properties of PLA did not improve at any concentration of MA in ENR-g-MA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48297.     

Thermoplastic vulcanizates based on poly(methyl methacrylate)/epoxidized natural rubber blends: Mechanical,thermal, and morphological properties

Epoxidized natural rubbers (ENRs) with epoxide levels of 10, 20, 30, 40 and 50 mol % were prepared. The ENRs were later used to prepare thermoplastic vulcanizates (TPVs) by blending them with poly(methyl methacrylate) (PMMA) using various formulations. Dynamic vulcanization, using sulfur as a vulcanizing agent, was performed during the mixing process. The mixing torque increased as the ENR contents and epoxide molar percentage increased. This was because of an increasing chemical interaction between the polar groups of the blend components, particularly at the interface between the elastomeric and thermoplastic phases. The ultimate tensile strength of the TPVs with ENR‐20 was high because of strain‐induced crystallization. ENRs with epoxide levels >30 mol % exhibited an increase of tensile strength because of increasing levels of chemical interaction between the molecules and the different phases. The hardness of the TPVs also increased with increased epoxide levels but decreased with increased contents of ENRs. Two morphology phases with small domains of vulcanized ENR particles dispersed in the PMMA matrix were observed from scanning electron microscopy micrographs. The TPVs based on ENR‐20 and ENR‐50 showed smaller dispersed rubber domains than those of the other types of ENRs. Furthermore, the size of the vulcanized rubber domain decreased with increasing amounts of PMMA in the blends. The decomposition temperature of the TPVs also increased as both the levels of ENRs in the blends and the epoxide molar percentage increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1251–1261, 2005     

Miscibility of poly(vinyl alcohol)/polyacrylamide blends before and after gamma irradiation

Films of polymer blends having various contents of poly(vinyl alcohol) (PVA) and polyacrylamide (PAM) were prepared by the solution casting technique using water as a common solvent. The thermal, mechanical and morphological properties of these blends before and after exposure to various doses of gamma radiation, up to 100 kGy, have been investigated. The visual observation and reflectance measurements show that PVA/PAM blends are miscible over a wide range of composition. Moreover, the differential scanning calorimetry (DSC) thermograms show only a single glass transition temperature (T_g), but not those of PVA or PAM homopolymers, giving further support to the complete compatibility of such blends. The T_g of PVA/PAM blends decreases with increasing content of PAM but increases after exposure to gamma irradiation, indicating the occurrence of crosslinking. These findings were demonstrated by the scanning electron micrographs of the fracture surfaces and the tensile mechanical properties. The TGA thermograms and percentage mass loss at different decomposition temperatures show that unirradiated PVA homopolymer possesses higher thermal stability than PAM homopolymer and their blends within the heating temperature range investigated, up to 250 °C. An opposite trend is observed within the temperature range 300–500 °C. In general, the thermal stability of homopolymers or their blends improves slighly after exposure to an irradiation dose of 100 kGy. These findings are clearly confirmed by the calculated activation energies of the thermal decomposition reaction of the homopolymers and the blends. © 2003 Society of Chemical Industry