Morphological reorganization and mechanical enhancement in multilayered polyethylene/polypropylene films by layer multiplication or mild annealing

Shortly after processing, Polyethylene/Polypropylene (PE/PP) multilayer films demonstrate an increase in tensile modulus and other mechanical properties when the individual layer thickness is below 0.5 µm. Subsequent annealing at 60 °C for 16 h brings the properties of all other samples to similar values. WAXD characterization of the layered films identified a prevalence of mesophase in the thicker PP layers. In samples with increased layer numerosity or subjected to annealing, WAXD detected its conversion to α crystalline phase that correlates with improved mechanical properties. SSNMR and DSC detailed the defective nature of α iPP crystallites. Comonomers, detected by NMR in the commercial polymers used for the films, are the source of “tunable disorder” that dictates the formation of the PP mesophase and the low temperature of conversion to the mechanically stronger defective α phase. Soft intrafilm layer interfaces instead enable nucleation and localized polymer chain rearrangement even without annealing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 520–531     

Crystallization of the mesomorphic form and control of the molecular structure for tailoring the mechanical properties of isotactic polypropylene

The combination of the control of the concentration of stereodefects in isotactic polypropylene using metallocene catalysts and the crystallization via the mesophase is a strategy to tailor the mechanical properties. Stiff materials, flexible materials, and thermoplastic elastomers can be produced depending only on the concentration of rr stereodefects. Modulus, ductility, and strength can be modulated through the crystallization of α and γ forms or of the mesophase. Different morphologies are observed depending on the stereoregularity and conditions of crystallization. Crystals of the mesomorphic form always exhibit a nodular morphology, accounting for the similar good deformability of all quenched samples, whatever the concentration of stereodefects. The mesophase transforms by thermal treatments into the α form preserving the nodular morphology, with increase of strength while maintaining the ductility typical of the mesophase. Annealing of the mesophase permits a precise adjustment of crystallinity and size of nodular crystals offering additional options to modify the mechanical properties. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 677–699     

Synthesis and characterization of iPP‐sPP stereoblock produced by a binary metallocene system

Stereoblock polypropylenes comprising of iPP and sPP segments are synthesized by polymerization of the following binary system of metallocenes: the C_s‐symmetric [2,7‐t‐Bu₂(Flu)₂Ph₂C(Cp)ZrCl₂] and the C₂‐symmetric rac‐Me₂Si(2‐Me‐4‐Ph‐Ind)₂ZrCl₂. Blends of samples made either by each catalyst individually (solution blend) with materials obtained with the mixed catalyst system (reactor blend) are compared. The simultaneous presence of MAO and DEZ, enhancing fast and reversible transfer of the growing chains between the two active centers, leads to the formation of a stereoblock microstructure. In this case, low molecular weight polymers are obtained. The junction between the blocks is qualitatively observed in ¹³C NMR. When made in toluene, the stereoblock material consists of a majority of syndiotactic sequences, whereas the ratio is more equilibrated when the polymerization was conducted in the more polar chlorobenzene. This is confirmed by the results obtained with ¹³C NMR, CRYSTAF, HT HPLC, DSC, SSA, WAXD, and optical microscopy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1422–1434     

PP/ABS合金的制备及不同阻燃剂对其性能的影响

选用过氧化二异丙苯(DCP)作为交联剂,三烯丙基异氰脲酸酯(TAIC)作为助交联剂,在密炼机里熔融共混制备PP/ABS合金.对制得的产物进行红外光谱、扫描电镜测试.结果表明最佳的添加量为DCP 0.2%(质量分数),TAIC4%(质量分数);在制得的PP/ABS合金的基础上,先单独添加阻燃剂N,N-四溴邻苯二甲酰亚胺(BT-93W),然后进行BT-93W和阻燃增效剂2,3-二甲基-2,3-二苯基丁烷(DMDPB)复合添加,对制得的两种复合材料进行力学性能、极限氧指数、垂直燃烧实验测试.结果表明:阻燃协效剂DMDPB复合BT-93W使用时,在不影响阻燃性能的情况下,能大幅度减少BT-93W的用量,减少其对材料力学和加工性能的影响.     

Morphological,Thermal, and Electrical Characterization of Syndiotactic Polypropylene/Multiwalled Carbon Nanotube Composites

In this work, syndiotactic polypropylene/multiwalled carbon nanotubes (MWCNT) nanocomposites, in various concentrations, were produced using melt mixing. The influence of the addition of MWCNT on the morphology, crystalline form, and the thermal and electrical properties of the polymer matrix was studied. To that aim, scanning electron microscopy, Raman spectroscopy, X-ray diffraction, differential scanning calorimetry, and dielectric relaxation spectroscopy were employed. Significant alterations of both the crystallization behavior and the thermal properties of the matrix were found on addition of the carbon nanotubes: conversion of the disordered crystalline form I to the ordered one, increase of the crystallization temperature and the degree of crystallinity, and decrease of the glass transition temperature and the heat capacity jump. Finally, the electrical percolation threshold was found between 2.5–3.0 wt.% MWCNT. For comparison purposes, the results of the system studied here are also correlated with the findings from a previous work on the isotactic polypropylene/MWCNT system.     

ESSENTIAL WORK OF FRACTURE AND THE PHASE TRANSFORMATION IN β-iPP

The possibility of phase transformation toughening is demonstrated by the example of the β-modification isotactic polypropylene (β-iPP), which undergoes the β–α transformation (i.e., from hexagonal to monoclinic) during mechanical loading. The β–α recrystallization was examined on essential work of fracture (EWF) specimens with two processing conditions. Differential scanning calorimetry and wide-angle x-ray diffraction demonstrate the occurrence of this β–α transformation. Some structural changes can be identified in EWF specimens by using nano-indentation machine. Toughness of the α- and β-iPP is studied and compared with the EWF concept by using static-loaded deeply double-edge-notched tensile specimens. The main effect of the β–α transformation is a large increase in the specific plastic work consumed in the necked zone.     

聚丙烯成核剂研究进展

聚丙烯的改性在其实际生产应用中有重要作用.在聚丙烯中添加成核剂可以改善聚丙烯的物理机械性能,达到聚丙烯改性的目的.介绍了聚丙烯成核剂的作用机理,以及聚丙烯的α晶成核剂和β晶成核剂的特点、作用效果及对聚丙烯性能的影响.     

Thermal Behavior of Polypropylene-g-glycidyl Methacrylate Prepared by Melt Grafting

The thermal behaviors of glycidyl methacrylate (GMA)-grafted polypropylene (PP) (PP-g-GMA) with two different grafting degrees, namely, GPP1 and GPP2, were investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA), and thermogravimetrical analysis (TGA). DSC results suggested that the GMA grafted PP exhibited higher crystallization temperature T_c, higher melting temperature T_m, and higher crystallinity compared with the neat PP. The isothermal crystallization kinetics was analyzed with the Avrami equation and the total crystallization activation energy was calculated. It was concluded that the crystallization processes of PP and the grafted PP were controlled by nucleation and the values of the crystallization activation energy of PP and the grafted PP were almost identical. POM results suggested that the GMA grafted PP exhibited smaller spherulites size compared with the neat PP. WAXD patterns indicated that the neat PP encouraged the formation of γ phase, compared with the grafted PP, during the crystallization process. DMA results showed that melt grafting did not induce a clear effect on the γ-transition and β-transition of the amorphous phase but resulted in a decrease in mobility of the PP chains in the crystals. TGA curves suggested that the melt grafting slightly improved the thermal stability of PP.     

Metallocenes with Cp Ring-Fused to Chalcogen Heterocycles: Synthesis and Polymerization Results

Abstract

Substituted metallocene ligands containing cyclopentadiene ring fused to either selenophene or benzo[b]tellurophene were prepared following methods previously developed for analogs containing sulfur. 5-Methyl-4,5-dihydro-cyclopenta[b]-selenophen-6-one ( 2 ) and 3-Methyl-3,4-dihydro-benzo[b]cyclopenta[d]telluraphen-2-one ( 7 ) (major isomers) were prepared by polyphosphoric acid catalyzed Friedel-Crafts acylation/Nazarov cyclization of methacrylic acid onto selenophene and respectively benzo[b]tellurophene. Following reduction of the ketone to alcohol, then dehydration, the chalcogen-containing cyclopentadiene olefins were prepared. The olefins were deprotonated with n-butyllithium followed by either bridging with dichlorodimethylsilane, deprotonation and metallation, or deprotonation and direct metallation. In this manner, isomeric mixtures of –rac/-meso dimethylsilanediylbis(η⁵-5-Methyl-cyclopenta[b]selenophen-yl)zirconium dichloride ( 5 ) Bis(η^5?2-methyl-cyclopenta[b][1 Brintzinger, H. H., Fischer, D., Mülhaupt, R., Rieger, B. and Waymouth, R. 1995. Angew. Chem., 107: 1255[Crossref] , [Google Scholar]]benzotelluraphen-yl)zirconium dichloride ( 9 ) were prepared and characterized. Complexes formed active olefin polymerization catalyst when activated with methylalumoxane. Polymerization results with ethylene and propylene are included.