Melt-Miscible Oxalamide Based Nucleating Agents and Their Nucleation Efficiency in Isotactic Polypropylene

Deshmukh, Yogesh S.; Wilsens, Carolus H. R. M.; Leoné, Nils; Portale, Giuseppe; Harings, Jules; Rastogi, Sanjay

doi:10.1021/acs.iecr.6b03120

Cited by 14 publications

(39 citation statements)

References 43 publications

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“… 31 For example, in previous work we demonstrated that shearing i PP systems blended with OXA3,6 increased the onset of crystallization from 123 to 140 °C, making it comparable to other organic nucleating agents such as the sorbitol derived nucleating agent DMDBS. 4 This synergetic effect between the nucleating efficiency of OXA 3,6 and shear is believed to be similar to that of sheared systems that contain (nucleating) nanoparticles. 15 , 19 , 32 − 36 In general, this synergy is attributed to the enhancement of the flow effect on the polymer kinetics and morphology.…”

Section: Resultsmentioning

confidence: 80%

“…It has been earlier reported by us that the OXA3,6 nucleating agent crystals provide a surface for nucleation, which on shear alignment will provide the required orientation facilitating the transcrystallization morphology. 4 For this reason, we attribute the kebab crystal growth observed after the application of low γ̇ to the shear-alignment of the OXA3,6 crystals. A further increase in the L p to 22.7 nm is observed only after the application of a shear pulse with γ̇ ≥ 100 s –1 , indicating the presence of a shear-induced shish-kebab morphology.…”

Section: Resultsmentioning

confidence: 99%

“…The nucleating agent OXA3,6 has been synthesized as described in a previous publication. 4 All materials were dried in vacuo at 80 °C overnight, prior to processing. Extrusion and blending were performed at 220 °C for 3 min at 100 rpm in a single-screw extruder.…”

Section: Experimental Sectionmentioning

confidence: 99%

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Effect of Self-Assembly of Oxalamide Based Organic Compounds on Melt Behavior, Nucleation, and Crystallization of Isotactic Polypropylene

et al. 2018

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We report on the effect of an aliphatic oxalamide based nucleating agent (OXA3,6) on the melt and crystallization behavior of isotactic polypropylene (iPP) under defined shear conditions. Through polarized optical microscopy, we demonstrate that OXA3,6 self-assembles from the iPP melt into rhombic crystals whereas their size and distribution proved highly dependent on the employed cooling rates. The presence of 0.5 wt % of OXA3,6 in iPP results in a significant suppression in iPP melt viscosity, which could not be explained via molecular modeling. A possible cause for the drop in viscosity in the presence of OXA3,6 is attributed to the interaction (absorption) of high molecular weight iPP chains with the nucleating agent, thereby suppressing their contribution to the viscoelastic response of the melt. This proposed mechanism for the suppression in melt viscosity appears similar to that encountered by the homogeneous distribution of nanoparticles such as CNTs, graphene, and silica. Shear experiments, performed using a slit flow device combined with small-angle X-ray diffraction measurements, indicate that crystallization is significantly enhanced in the presence of OXA3,6 at relatively low shear rates despite its lowered sensitivity to shear. This enhancement in crystallization is attributed to the shear alignment of the rhombic OXA3,6 crystals that provide surface for iPP kebab growth upon cooling. Overall, the suppression in melt viscosity in combination with enhanced nucleation efficiency at low as well as high shear rates makes this self-assembling oxalamide based nucleating agent a promising candidate for fast processing.

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Section: Resultsmentioning

confidence: 80%

Section: Resultsmentioning

confidence: 99%

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Effect of Self-Assembly of Oxalamide Based Organic Compounds on Melt Behavior, Nucleation, and Crystallization of Isotactic Polypropylene

et al. 2018

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“…Because the self-assembly of OXA3,6 proceeds via a nucleation and growth mechanism, the resultant particle morphology is found to be strongly dependent on parameters such as the application of shear, concentration, and cooling rates (Figure 1C). 10,24…”

Section: Introductionmentioning

confidence: 99%

Effect of Thermal History and Shear on the Viscoelastic Response of iPP Containing an Oxalamide-Based Organic Compound

et al. 2019

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We report on the role of temperature and shear on the melt behavior of iPP in the presence of the organic compound N1,N1′-(propane-1,3-diyl)bis(N2-hexyloxalamide) (OXA3,6). It is demonstrated that OXA3,6 facilitates a viscosity suppression when it resides in the molten state. The viscosity suppression is attributed to the interaction of iPP chains/subchains with molten OXA3,6 nanoclusters. The exact molecular mechanism has not been identified; nevertheless, a tentative explanation is proposed. The observed viscosity suppression appears similar to that encountered in polymer melts filled with solid nanoparticles, with the difference that the OXA3,6 compound reported in this study facilitates the viscosity suppression in the molten state. Upon cooling, as crystal growth of OXA3,6 progresses, the decrease in viscosity is suppressed. Retrospectively, segmental absorption of iPP chains on the surface of micrometer-sized OXA3,6 crystallites favors the formation of dangling arms, yielding OXA3,6 crystallites decorated with partially absorbed iPP chains. In other words, the resulting OXA3,6 particle morphology resembles that of a hairy particle or a starlike polymer chain. Such hairy particles effectively facilitate a viscosity enhancement, similar to branched polymer chains. This hypothesis and its implications for the shear behavior of iPP are discussed and supported using plate–plate rheometry and slit-flow experiments combined with small-angle X-ray scattering analysis.

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“…Nevertheless, only very few NAs are operational from commercial perspective. Frequent attempts have been made to explore the new structure NAs as well as to study the mechanism of heterogeneous nucleation . Bhatia et al reported that metal glycerolate platelets were highly effective NAs for iPP and the nucleation occurred epitaxially from platelet edges .…”

Section: Introductionmentioning

confidence: 99%

Effect of the Metal Phenylphosphonates on the Nonisothermal Crystallization and Performance of Isotactic Polypropylene

Jiang

Zhao

Meng

et al. 2018

J Polym Sci B Polym Phys

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The use of metal phenylphosphonates as efficient nucleating agents (NAs) for isotactic polypropylene (iPP) is reported and a possible structural correlation to the nucleation efficiency is studied. First, three kinds of metal phenylphosphonates are synthesized via reflux method: Ca(C 6 H 5 PO 3 )•2H 2 O (CaPPA), Ca(C 6 H 5 PO 3 H) 2 (CaPPA2), and Al(HO 3 PC 6 H 5 )(O 3 PC 6 H 5 ) •H 2 O (AlPPA2). Then, the nonisothermal crystallization behaviors, mechanical, and optical properties of iPP composites are investigated. Compared to CaPPA2 and AlPPA2, CaPPA exhibits more effective heterogeneous nucleation effect during iPP crystallization. Furthermore, the nucleation efficiency of CaPPA is similar to industrial standard NAs NA-21 and NA-11. With the addition of 0.1 wt % CaPPA, the crystallization temperature is enhanced and the parameter F(T) of Mo method is decreased appreciably. Moreover, the flexural modulus, impact strength, and haze values of iPP composites are improved remarkably by introducing CaPPA. The CH/π interaction between polymer and aromatic cleft of CaPPA is considered to facilitate the attachment of iPP chains and subsequent nucleation and crystallization, which is verified by the viscoelastic properties of pure iPP and composites. ) (PP) focused on the application of metal phosphonates as NAs for iPP. 25,26 Due to the potential ability to be effective NAs, it is necessary to synthesize appropriate metal phosphonates that Additional Supporting Information may be found in the online version of this article.

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Melt-Miscible Oxalamide Based Nucleating Agents and Their Nucleation Efficiency in Isotactic Polypropylene

Cited by 14 publications

References 43 publications

Effect of Self-Assembly of Oxalamide Based Organic Compounds on Melt Behavior, Nucleation, and Crystallization of Isotactic Polypropylene

Effect of Self-Assembly of Oxalamide Based Organic Compounds on Melt Behavior, Nucleation, and Crystallization of Isotactic Polypropylene

Effect of Thermal History and Shear on the Viscoelastic Response of iPP Containing an Oxalamide-Based Organic Compound

Effect of the Metal Phenylphosphonates on the Nonisothermal Crystallization and Performance of Isotactic Polypropylene

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