Modification of poly(vinyl alcohol) films by the addition of magnesium chloride hexahydrate

Poly(vinyl alcohol) (PVA) films modified with Magnesium chloride hexahydrate (MgCl₂·6H₂O) were prepared by casting method. The prepared films were characterized by X‐ray diffraction measurements (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and mechanical testing. It was found that the presence of MgCl₂·6H₂O had considerable effects on the crystallinity, thermal, and mechanical properties of PVA films. The crystallization of PVA film was interrupted and the degree of crystallinity of PVA film decreased with the addition of MgCl₂·6H₂O. The glass transition temperature of PVA film decreased with the addition of MgCl₂·6H₂O. After modifying with MgCl₂·6H₂O, PVA film became soft, with lower tensile strength and higher elongation at break. The presence of MgCl₂·6H₂O could significantly increase the moisture content of PVA films and this may be the cause of the plasticizing. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Polycaprolactone as a permanent plasticizer for poly(vinyl chloride)

Polycaprolactone at moderate usage levels has been determined to provide desirable modifications of both rigid and plasticized poly(vinyl chloride). In rigid PVC it effected significant improvement in melt processing as well as good modulus, tensile strength, and kerosene resistance. Impact strength was not measurably altered, but heat-distortion temperature was appreciably lowered. In flexible PVC, polycaprolactone contributed increased tensile strength and ultimate elongation, reduced volatility, and kerosene extraction. Lowering of modulus and flex temperatures were similar to conventional liquid polymeric plasticizers, but melt processability was not as good as lower-molecular-weight plasticizers.     

Poly(ethylene glycol)–polyhedral oligomeric silsesquioxane as a novel plasticizer and thermal stabilizer for poly(vinyl chloride) nanocomposites

The plasticizing and thermostabilizing effect of poly(ethylene glycol)–polyhedral oligomeric silsesquioxane (PEG‐POSS) on poly(vinyl chloride) (PVC) is discussed thoroughly in this work. As PEG‐POSS content increases, PVC becomes more flexible and the decomposition temperature of PVC increases slightly. Meanwhile, the temperature of maximum HCl emission is elevated from 265.3 °C in neat PVC to 285.7 °C in PVC nanocomposites, with the peak intensity of HCl emission decreased by 30.8%, and a new lower intensity of HCl emission peak appearing at much higher temperature (around 370 °C), which is in accordance with the maximum degradation temperature of PEG‐POSS. Thereby, a possible dehydrochlorination mechanism is suggested according to the fact that the electron donor effect of ether groups would stabilize the C? Cl bonds by means of more electron cloud stacked in those bonds, which agrees with Fourier transform infrared and X‐ray photoelectron spectroscopy experiments in terms of hydrogen bonds. © 2016 Society of Chemical Industry     

Chlorinated atactic polypropylene as a plasticizer for poly(vinyl chloride)

Atactic polypropylene, a byproduct obtained in the manufacture of isotactic polypropylene, has been chlorinated under various reaction conditions. The chlorination reaction is reasonably fast so as to give a product of 53-43% chlorine content in 3 h. The chlorinated product has been incorporated in poly(viny1 chloride) formulations with a view to study its plasticizing activity. Generally this type of compound acts only as a secondary plasticizer; hence it has been used in combination with di(2-ethylhexyl)phthdate, a primary plasticizer. Different proportions of these two plasticizers have been added to poly(vinyl chloride) resin to obtain a series of formulations. These compounds were evaluated, and it appears that the addition of chlorinated atactic polypropylene (APPC) helps in easy processing and increases the throughput. The increasing concentration of APPC showed an upward trend in die head pressure and torque indicating an increase in melt viscosity. The results of physical properties evaluation show that APPC acts as a reinforcing agent and also imparts permanence to the plasticizers.     

Synthesis of a secondary plasticizer for poly(vinyl chloride) by recycling of poly(ethylene terephthalate) bottle waste through aminolytic depolymerization

This study focuses on the synthesis and application of didecanoate of bis(3‐hydroxypropyl) terephthalamide (DD‐BHPTA) as a secondary plasticizer in poly(vinyl chloride) (PVC) compounding. DD‐BHPTA was synthesized from poly(ethylene terephthalate) bottle waste through aminolysis followed by condensation reaction with decanoic acid. Synthesized DD‐BHPTA was characterized by Fourier‐transform infrared spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance. Plasticized PVC was prepared by compounding PVC in different ratios with DD‐BHPTA and dioctyl phthalate (DOP) using a two‐roll mill. This newly synthesized plasticizer completely fused with PVC. The mechanical, thermal, and rheological properties like glass transition temperature, tensile strength, % elongation, dynamic mechanical analysis, solvent resistance, accelerated ultraviolet weathering test for color stability, differential scanning calorimetry, and thermal gravimetric analysis of plasticized PVC were investigated. DD‐BHPTA along with DOP plasticizer demonstrated plasticization efficiency similar to that of DOP alone, with the same plasticizer loading. DD‐BHPTA was found to be the more efficient plasticizer when used in combination with DOP. Thus, DD‐BHPTA can be used as a secondary plasticizer for DOP and can substitute DOP up to 50% of plasticizer loading. J. VINYL ADDIT. TECHNOL., 23:152–160, 2017. © 2015 Society of Plastics Engineers     

Polyhedral oligomeric silsesquioxane as a novel plasticizer for poly(vinyl chloride)

This study focuses on investigating the use of polyhedral oligomeric silsesquioxanes (POSS) to plasticize poly(vinyl chloride) (PVC). Conventional organic plasticizers for PVC, such as dioctyl phthalate (DOP), are somewhat volatile, leading to plasticizer loss and unwanted deterioration of the material properties over time. Previous experimental results indicate that methacryl-POSS, which is much less volatile due to its hybrid organic-inorganic structure, has the ability to plasticize PVC. Methacryl-POSS is miscible in the PVC only up to 15 wt%, thereby limiting its suitability as a plasticizer. However, through the use of ternary compositions it is possible to increase the proportion of methacryl-POSS in PVC substantially. The T_g of appropriately formulated ternary PVC/POSS/DOP compounds can be reduced to near room temperature, and these materials exhibit desirable ductile behavior. Binary (PVC/DOP) and ternary (PVC/POSS/DOP) compounds formulated to the same T_g values showed considerably different mechanical properties. Such findings reveal the possibility of using POSS to engineer the mechanical properties of plasticized PVC.     

Glycerol-modified poly(vinyl alcohol)/poly(ethylene glycol) self-healing hydrogel for artificial cartilage

Poly(vinyl alcohol) (PVA) hydrogels have shown potential applications in bionic articular cartilage due to their tissue-like viscoelasticity, good biocompatibility and low friction. However, their lack of adequate mechanical properties is a key obstacle for PVA hydrogels to replace natural cartilage. In this study, poly(ethylene glycol) (PEG) and glycerol were introduced into PVA, and a PVA/PEG–glycerol composite hydrogel was synthesized using a mixing physical crosslinking method. The mechanical properties, hydrophilicity and tribological behavior of the PVA/PEG–glycerol hydrogel were investigated by changing the concentration of glycerol in PEG. The results showed that the tensile strength of the hydrogel reached 26.6 MPa at 270% elongation at break with 20 wt% of glycerol plasticizer, which satisfied the demand of natural cartilage. In addition, the excellent hydrophilicity of glycerol provides good lubricating properties for the composite gel under dry friction. Meanwhile, self-healing and cellular immunity assays demonstrated that the composite gel could have good self-healing ability and excellent biocompatibility even in the absence of external stimuli. This study provides a new candidate material for the design of articular cartilage, which has the potential to facilitate advances in artificial joint cartilage repair. © 2022 Society of Industrial Chemistry.     

Melt viscosity of poly(vinyl chloride) formulations

Commercial, suspension-type PVC resin, poly (vinyl chloride), molecular weight M_w × 10^?4 = 8.6 ± 0.9, polydispersity M_w/M_n = 2.26, was mixed with plasticizer di(2-ethyl hexyl)phthalate (DOP) and organo-tin stabilizer in four different proportions. The mixtures were milled and pressed into sheets for testing. The polymer content in these samples was 97, 80, 60, and 40 wt percent. The viscoelastic properties of the materials were investigated using a Weissenberg rheogoniometer in a cone-and-plate, steady-state shearing mode. The viscosities and primary normal stress difference coefficients were measured at shear rates of 10^?2 ≤ \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop \gamma \limits^. $\end{document} (sec^?1) ≤ 10² and at temperatures from 151 to 246°C. The zero shear viscosities, plotted as log η₀ vs 1/T (T is the absolute temperature) did not follow either a straight line dependence, reported for PVC melts at low shear rates at 170–190°C, nor was any discontinuity found near 195°C as by others; the data follows a continuous concave curve. The apparent activation energy of flow increases steeply with decreasing temperature. The data can be represented by a WLF type of equation, but the magnitudes of the parameters of this relation differ from expected values. A crossplot of log η₀ (T = const.) vs log w (where w is the polymer content) also demonstrates a faster increase of η₀ with w than expected from the straight line dependence. The primary normal stress difference coefficient was found to increase with w and decrease with T, paralleling the observed dependencies of η₀.     

Migration resistant polymeric plasticizer for poly(vinyl chloride)

Flexible films of poly(vinyl chloride) (PVC) and linear or branched poly(butylene adipate) (PBA), synthesized from 1,4‐butanediol and adipic acid or dimethyl ester of adipic acid, were aged in an aqueous environment for 10 weeks to study how branching, molar mass, and end‐group functionality affect the leaching of polyester plasticizer from thin films. Principal component analysis was applied to reveal patterns and correlations between mechanical properties, material characteristics, and aging behavior. Introduction of branches in the polyester structure increased the miscibility between PVC and the polyester, resulting in improved mechanical properties and lower water absorption. Methyl ester end‐group in PBA polyester stabilized the polymeric plasticizer toward hydrolysis, and reduced the formation and migration of monomeric degradation products from the blends during aging in water. The combination of branched structure with methyl ester end‐groups resulted in a migration resistant polymeric plasticizer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2458–2467, 2007     

Alloying of poly(vinyl chloride) to reduce plasticizer migration

Concern over the migration of low molecular weight plasticizer from flexible poly(vinyl chloride) (PVC) used in toys and medical products has spearheaded the commercialization of a number of plasticizing polymers. In this study the plasticizing behavior of an ethylene/vinyl acetate/carbon monoxide terpolymer (Elvaloy® from DuPont) was investigated. Blends of PVC, Elvaloy 742, and dioctyl phthalate (DOP) were processed on a twin‐roll mill and compression molded into plaques. These materials were characterized in terms of their hardness, glass‐transition temperature (T_g), clarity, mechanical properties, and plasticizer migration behavior. The ratios of PVC/DOP/Elvaloy investigated were determined by experimental design. Using this approach it was possible to model the results and produce contour plots to map out the properties of a wide range of formulations. It was confirmed that Elvaloy 742 is compatible with PVC and has a plasticizing effect: this was demonstrated both in terms of a reduction in Shore A hardness and a reduction in T_g. Plasticizer migration was reduced in proportion to the amount of liquid plasticizer replaced. Plasticizing with Elvaloy gave an improvement in tear strength. However, at constant hardness there was no improvement in tensile strength from replacing DOP with Elvaloy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2022–2031, 2004     

Epoxidized rice bran oil (ERBO) as a plasticizer for poly(vinyl chloride) (PVC)

With environmental and toxicity concerns becoming more critical, there are increasing efforts to remove phthalates from polymer compounds around the globe more rapidly. Phthalates can be replaced by natural products; in particular, those obtained from vegetable oils and fats. In the present study, a natural-based plasticizer, synthesized by epoxidation of non-toxic rice bran oil (RBO) with peroxy acid generated in situ has been added to poly(vinyl chloride). The influence of various reaction parameters on epoxidation was studied by investigating the reaction ratio, temperature, reaction time and stirring speed. Epoxidized rice bran oil (ERBO) obtained from an optimized reaction condition was analyzed by iodine number and oxirane content. FTIR was used to analyze epoxy group formation. Product ERBO was obtained with 82 % oxirane conversion within 3 h of reaction period. PVC sheets were formulated using a conventional plasticizer di-(octyl) phthalate and was partially replaced by synthesized ERBO. The effect of ERBO addition was tested by mechanical properties (tensile strength, modulus, elongation-at-break, shore D hardness) and compared with commercially available ESBO (epoxidized soybean oil). ERBO presented fairly good incorporation and plasticizing performance, as demonstrated by the results of mechanical properties, exudation, migration tests, thermal stability by thermogravimetric analysis, T _g values as shown by differential scanning calorimetry, replacing about 60 % of the total plasticizer.     

Synthesis of glycidylethylhexylphthalate and its effects on poly(vinyl chloride) films as a novel plasticizer

To improve the processability and prevent the thermal degradation of poly(vinyl chloride) (PVC), various plasticizers and heat stabilizers have to be compounded. Phthalic plasticizers and metal soap stabilizers are usually used with epoxides as costabilizers. Epoxidized soybean oil (ESO), is one of the most commonly used epoxides because of its typical combined roles as a plasticizer and heat stabilizer in PVC compounds. ESO, however, sometimes causes surface contamination of PVC compounds because saturated fatty acids such as stearic and palmitic acids in soybean oil easily bleed onto the surface. In addition, some ingredients in ESO with hydroxide groups and unreacted double bonds during epoxidization also tend to increase the bleeding of ESO. This is due to their low compatibility with PVC resins. In this study, a novel plasticizer of PVC resins, glycidylethylhexylphthalate (GEHP), was synthesized, and its performance was evaluated. GEHP was designed to act as a plasticizer like normal phthalic plasticizers and to act as a heat stabilizer like ESO. Through the addition of epoxy groups in phthalic compounds, the resistance to bleeding was improved, and the plasticizing and heat‐stabilizing effects on the PVC compounds were preserved. Soft PVC films were prepared with GEHP. The mechanical properties, thermal stability, and bleeding properties of the films were investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1347–1356, 2005     

Studies on aluminum-isopropoxide doped poly(ethylene oxide), poly(vinyl alcohol), and poly(ethylene oxide)-poly(vinyl alcohol) blends

Poly(ethylene oxide), poly(vinyl alcohol), and their blend in a 40 : 60 mole ratio were doped with aluminum isopropoxide. Their structural, thermal, and electrical properties were studied. Aluminum isopropoxide acts as a Lewis acid and thus significantly influences the electrical properties of the polymers and the blend. It also acts as a scavanger for the trace quantities of water present in them, thereby reducing the magnitude of proton transport. It also affects the structure of polymers that manifests in the thermal transformation and decomposition characteristics. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2147–2157, 1998     

The effect of microwave irradiation on poly(vinyl alcohol) dissolved in ethylene glycol

Poly(vinyl alcohol) (PVA) dissolved in ethylene glycol is subjected to microwave (MW) irradiation for 1 h to determine possible degradation. Fourier transform infrared spectroscopy results show that MW treatment produces a minor effect on the solutions. Ultraviolet–visible spectroscopy suggests that PVA could undergoes loss of hydroxyl groups followed by formation of unsaturated conjugated bonds although the extent of degradation is limited, whereas size exclusion chromatography indicates that MW irradiation do not cause significant changes in PVA molar mass and neither chain cleavage nor crosslinking reactions are observed. Hence, polymer degradation induced by MWs in solution can be considered as negligible for prospective applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇（X-PEG-X）大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯（VC）溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯（PVC-b-PEG-b-PVC）三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯（VAc）扩链反应进一步证实了PVC-b-PEG-b-PVC的“活性”,并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。     

Crystallinity,reversibility, and injectability of physically crosslinked poly(vinyl alcohol) and poly(ethylene glycol) hydrogels

Crystallite regions within a hydrogel network contribute to its mechanical strength, which is crucial for use in load-bearing applications. However, high amounts of crystallinity can negatively impact the ability for hydrogels to be injected, an attractive property that could replace the need for highly invasive surgical procedures. The reversibility of crystallinity and its lasting impact on the injectability of poly(vinyl alcohol) and poly(ethylene glycol) hydrogels was evaluated in this paper. The relative percent crystallinity in hydrogels was evaluated after storage and autoclaving in syringes in weekly intervals using X-ray diffraction. Results indicate that crystallinity increased over time and significantly decreased after autoclaving for all samples, where postautoclaved samples contained comparable crystallinity percentages to freshly made gels (p > 0.05). Injectability was evaluated using calculated viscosity. Aged samples were able to be injected after autoclaving, yet there was no determination established between viscosity and storage times based on the data. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48706.     

The effect of poly(ethylene glycol) as plasticizer in blends of poly(lactic acid) and poly(butylene succinate)

The effect of polyethylene glycol (PEG) on the mechanical and thermal properties of poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blends was examined. Overall, it was found that PEG acted as an effective plasticizer for the PLA phase in these microphase‐separated blends, increasing the elongation at break in all blends and decreasing the T_g of the PLA phase. Significant effects on other properties were also observed. The tensile strength and Young's modulus both decreased with increasing PEG content in the blends. In contrast, the elongation at break increased with the addition of PEG, suggesting that PEG acted as a plasticizer in the polymer blends. Scanning electron microscope images showed that the fracture mode of PLA changed from brittle to ductile with the addition of PEG in the polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43044.     

Gelation of poly(vinyl alcohol)/ethylene glycol solutions and properties of gels

The melting temperature of the gels of the poly(vinyl alcohol) (PVA)/ethylene glycol (EG) system was measured. It was found that the temperature was independent of the thermal hysteresis. The apparent enthalpy of the fusion of the junction, ΔH, was 206 kJ/mol for a high molecular weight atactic PVA (HDP α-PVA), 172 kJ/mol for a low molecular weight syndiotacticity-rich PVA (LDP s-PVA), and 238 kJ/mol for an HDP s-PVA. The gels obtained by chilling at temperatures over 80°C or by gradual cooling are considered to have larger microcrystals. The Young's modulus of the HDP α-PVA drawn films were highest among the samples tested. The maximum and mean Young's moduli of the HDP α-PVA films drawn 15 times the original length were 37 and 26 GPa, respectively. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1283–1289, 1997