Bharat Indu Chaudhary

Vinyltrimethoxysilane (VTMS) functionalized ethylenic polymers, in the form of reactor‐made ethylene‐silane copolymers as well as post‐reactor made silane‐grafted ethylene polymers, were evaluated for the purpose of moisture‐induced crosslinking through hydrolysis and condensation reactions. The copolymers were of 1.6 wt% or 4.2 wt% VTMS contents, and the silane‐grafted resins ranged in VTMS contents from 1.1 to 3.7 wt%. The silane‐grafted materials were very reactive under humid conditions at room temperature, resulting in very poor shelf stabilities manifested in sharp drops in their melt indices over time (changes that in the early stages were dominated mostly by resin molecular weight distribution and/or branching, and in the later stages much more by silane content). In sharp contrast, the ethylene‐silane copolymers exhibited outstanding shelf stabilities over time even at relatively high silane content, indicating desirably low reactivities in the absence of moisture‐cure catalyst. When formulated with catalyst, and exposed to humid conditions, the cure characteristics of the silane functionalized ethylene polymers varied significantly, with the fastest and greatest crosslinking observed using the ethylene‐silane copolymer of 4.2 wt% VTMS content and remarkably excellent shelf stability. Analyses of reaction rates revealed very interesting trends, depending on type of catalyst (tin or sulfonic acid) and resin.Highlights: Ethylene‐silane copolymers and silane‐grafted ethylene polymers were studied. Copolymers exhibited vastly superior shelf stabilities than grafted materials. Catalyst type and loading affected moisture‐induced crosslinkability. Increased silane content in copolymer led to faster and greater crosslinking. Best balance of crosslinkability and shelf stability obtained with copolymers.

Dialkyl furan‐2,5‐dicarboxylates and epoxidized fatty acid esters (EFAE) of varying molecular weights and volatilities, as well as their mixtures, were investigated as alternative plasticizers for poly(vinylchloride) (PVC). The EFAE utilized were epoxidized soybean oil (ESO) and epoxidized fatty acid methyl ester (e‐FAME). All plasticizers were compatible with PVC, with plasticization efficiencies usually increasing with decreasing molecular weights of the plasticizers (except in the case of ESO, which was remarkably effective at plasticizing PVC, in spite of its relatively high molecular weight). In comparison with phthalate and trimellitate plasticizers, the alternatives generally yielded improved balance of flexibility and retention of mechanical properties after heat aging, with particularly outstanding results obtained using 30−50 wt % e‐FAME in mixtures with diisotridecyl 2,5‐furandicarboxylate. Although heat aging characteristics of the plasticized polymer were often related to plasticizer volatilities, e‐FAME performed better than bis(2‐ethylhexyl) 2,5‐furandicarboxylate, and bis(2‐ethylhexyl) phthalate of comparatively higher molecular weights. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42382.

The efficacy of epoxidized soybean oil (ESO), tri(2‐ethylhexyl) trimellitate, and mixtures thereof as plasticizers for poly(vinylchloride) has been studied. At 80°C, the trimellitate was slower to absorb in this polymer than ESO and was also less soluble, but the former exhibited higher solubility at 120°C. Plasticization efficiencies of stabilized polymeric compositions were similar with ESO and the trimellitate (despite their very different molecular weights). The trimellitate yielded greater mass loss during heat aging of the plasticized compositions, but substituting even minor amounts of it with ESO decreased mass loss synergistically. The trimellitate also resulted in more of an increase in hardness than ESO over time at elevated temperatures, but when aged at 120°C, mixtures of the two surprisingly had more deleterious effects. Thus, although ESO can replace part or all of trimellitates in plasticized PVC, using it as sole plasticizer would be preferable when heat aging performance is a requirement. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41966.

Mixtures of bis(2‐ethylhexyl) succinate and epoxidized soybean oil (ESO) have been evaluated as bio‐based plasticizers for poly(vinylchloride). The rate of absorption of the bioplasticizers and their mixtures in the polymer was fast and, unlike that of petroleum‐derived plasticizers, did not vary significantly with molecular weight. These bio‐derived plasticizers and their mixtures were compatible with the polymer even at high loadings. The succinate was the most volatile and efficient plasticizer, but on heat aging of the polymer compositions, it also had the greatest deleterious effects. Diffusion coefficients and apparent activation energies of formulations containing bioplasticizer mixtures were controlled by the more volatile succinate. Mixtures comprising up to 50 wt% of the succinate yielded acceptably high‐tensile properties after thermal aging as well as better plasticization efficiency than the epoxy bioplasticizer. Although the succinate resulted in inferior volume resistivity of the polymer compositions, improvements were obtained with increasing proportions of the epoxidized derivative in plasticizer mixtures. Melt state viscosity‐shear rate curves of compositions containing dioctyl succinate (DOS) were similar to those made with two of the petroleum‐derived plasticizers, but a DOS/ESO mixture yielded extended non‐Newtonian behavior at low‐shear rates. POLYM. ENG. SCI., 55:634–640, 2015. © 2014 Society of Plastics Engineers

Thermal analyses of epoxidized soybean oil (ESO) were conducted and showed that it was stable up to temperatures as high as 240–260°C in air‐free environment. The solubility and transport characteristics of ESO in poly(vinylchloride) (PVC) were also investigated under various conditions. The absorption study showed that the resin had a void volume of ∼0.3 cm³/g. Furthermore, ESO was found to be sufficiently soluble in the PVC matrix to function as an effective plasticizer, with equilibrium solubility of 72 g/100 g PVC at 80°C and 163 g/100 g PVC at 120°C. The absorption of ESO in PVC grains was a three step process comprising “induction,” “swelling,” and “saturation” periods. Torque rheometer studies showed that higher mixer temperature and/or speed facilitated uptake of plasticizer in PVC and ultimate fusion. Migration studies of plasticized and stabilized PVC compositions showed no change in mass at 40°C, but increasingly greater mass loss as the temperature was raised up to 120°C. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers

The molded electrode test system (METS) test has long been used with flexible poly(vinyl chloride) (PVC) electrical insulation. However, there are many questions regarding its precision and accuracy, as there is no industry‐accepted standard regarding this test. This paper aims to answer some of these questions in terms of the measurement precision as well as the ability of the test to predict wet electrical performance on wire. A repeatability study was conducted on flexible PVC compound where 10 samples were produced and tested under identical conditions. The mean insulation resistance was (550 MΩ)/(305 m) with a standard deviation of (120 MΩ)/(305 m). As the thickness of the insulation increased, the insulation resistance decreased. Furthermore, the study showed that there was no correlation between the METS test and wet volume resistivity, while there was some correlation with wet insulation resistance (IR) at high temperature, though the ability to predict wet IR from the METS test was limited. J. VINYL ADDIT. TECHNOL., 18:178–183, 2012. © 2012 Society of Plastics Engineers

Different approaches for free‐radical initiated grafting of functional monomers to polypropylene (PP) have been investigated with a view to enabling crosslinking of the polymer upon subsequent exposure to moisture, resulting in gel contents as high as 50–60 wt%. The first approach involved grafting a co‐agent such as triallyl trimellitate (TATM) to the polymer using peroxide initiator to add carbon–carbon double bond functionality to the polymer, followed by peroxide‐initiated grafting of mercaptopropyltrimethoxysilane (MPTMS) to the PP‐TATM adduct. The second approach was the more traditional peroxide‐mediated grafting of vinyltrimethoxysilane (VTMS) to polypropylene, and was most effective at increasing melt state dynamic storage modulus. In the third approach, peroxide‐mediated grafting of VTMS was followed by peroxide‐initiated grafting of MPTMS. This process took advantage of the unsaturation created via chain scission in the first step to provide graft sites for the MPTMS in the second step. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers