Modifying the structure and properties of polyethylene foams using thermal treatments

BACKGROUND: The physical properties of polymer foams depend on many factors: density, cellular structure, matrix polymer morphology, etc. Therefore, these properties can be adapted by appropriate control of the structure. However, this simple and attractive concept has some limitations because the cellular structure of foams cannot be fully controlled during manufacturing. Therefore, in order to make possible the control of properties, it is highly desirable to develop simple procedures, such as thermal treatments, to modify the cellular structure. In the work reported, low‐density polyethylene foams were thermally treated at temperatures below the melting temperature of the base polymer. The cellular structure, polymer base morphology and several thermal and mechanical properties were studied before and after the thermal treatments. RESULTS: It is shown that the anisotropy of the cellular structure is reduced by using adequate treatments. This modification of the structure influences physical properties that are sensitive to the cell shape, such as thermal expansion, elastic modulus and collapse stress. CONCLUSION: A simple procedure to allow further control of the structure and properties of polyethylene‐based foams has been presented. The use of adequate thermal treatments is able to modify the cellular structure and hence the physical properties of these materials. Copyright © 2009 Society of Chemical Industry     

第二代聚烯烃技术

论述了对聚烯烃发展有重要影响的商效催化剂，技术，气相聚乙烯工艺中的冷凝态进料技术，双峰分子量分布树脂技术及在反应器中生产球形粒子树脂技术。对我国聚烯烃工业的发展提出了几点看法。     

Direct synthesis of highly reactive polyisobutylenes via cationic polymerization of isobutylene co‐initiated with TiCl4 in nonpolar hydrocarbon media

Living cationic polymerization of isobutylene (IB) with 1‐chlorine‐2,4,4‐trimethyl pentane (TMPCl)/TiCl₄/isopropanol (iPrOH) or isoamylol (iAmOH) has been achieved in the presence of 2,6‐di‐tert‐butylpyridine (DtBP) at ?80°C. Polyisobutylenes with nearly theoretical M_n based on TMPCl molecules and more than 90% of tert‐chlorine‐end groups could be obtained at high [TMPCl]. The β‐proton elimination from ? CH₃ in growing chain ends increased with increasing polymerization temperature and decreasing solvent polarity. A chain‐transfer‐dominated cationic polymerization process with H₂O/TiCl₄/iAmOH could be achieved in n‐hexane at ?30°C. The monomer conversion and content of exo‐olefin end groups increased while molecular weight decreased with increasing [iAmOH]. To the best of our knowledge, this is the first example to achieve the direct synthesis of highly reactive polyisobutylene with low M_n of 1200～1600, carrying more than 80% of exo‐olefin terminals by a single‐step process via cationic polymerization co‐initiated by TiCl₄ in nonpolar hydrocarbon. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42232.     

Preparation and characterization of polypropylene homocomposites: Exploiting polymorphism of PP homopolymer

In this study, the properties of polypropylene (PP) homocomposites, prepared by film‐stacking followed by hot pressing, were investigated. Alpha‐ and beta‐PP served as matrices, whereas highly oriented PP tapes of the alpha form acted as reinforcement in the homocomposites. Tapes with different draw ratios (DR = 6–12) have been produced and characterized by mechanical and wide‐angle X‐ray scattering measurements. Tapes with a DR = 8 were incorporated in a cross‐ply (CP) manner in the corresponding homocomposite laminates. Specimens were subjected to static (tensile, flexural) and dynamic (instrumented falling weight impact, IFWI) tests. The thermal and thermomechanical properties of the PP tapes and homocomposites were studied by differential scanning calorimetry and dynamic mechanical thermal analysis. The homocomposite morphology was probed by polarized light microscopy, which gave evidence of transcrystalline layer at the interface between tape and matrix. The storage modulus of the CP homocomposites was improved prominently by the tape reinforcement. In static tensile tests, the homocomposites exhibited much higher stiffness and strength when compared with the neat PP specimens. However, this was accompanied with a marked reduction in the ultimate elongation. The IFWI tests showed that both alpha‐ and the beta‐PP failed in macroscopically brittle manner, whereas the corresponding homocomposites failed in semiductile way. The homocomposite laminates prepared with beta‐PP matrix exhibited higher resistance to penetration than those with alpha‐PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Shrinkage in extruded moisture crosslinked silane‐grafted polyethylene wire insulation

Shrinkage studies were conducted on silane‐grafted moisture crosslinkable linear low‐density polyethylene (LLDPE) insulation stripped from extrusion‐coated copper conductors. The insulation, which possesses orientation imparted during melt processing, showed remarkable levels of shrinkage when heated above the melting point of the polymer, though the shrinkage can be greatly reduced by moisture crosslinking the insulation below the melting point of the LLDPE. Shrinkage along the direction of orientation was accompanied by swelling in the other dimensions. Differential scanning calorimetry (DSC) revealed several trends, including a decrease in both melting point and degree of crystallinity with increasing crosslinking. In the first heat after annealing, crosslinked samples exhibited a shoulder in the DSC endotherm several degrees below the normal melting point of the LLDPE. In agreement with prior studies in silane‐grafted HDPE, relaxation of orientation by annealing appeared to result in an increase in the enthalpy of melting. The degree of shrinkage was also found to be dependent on the insulation thickness, which is attributed to faster cooling in thinner insulation immediately following extrusion coating. The results highlight the extensive built in stresses that can be frozen into polymer layers in fabricated articles due to melt orientation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improvement of the surface quality of foam injection molded products from a material property perspective

Microcellular injection molding is an attractive method. However, their surface imperfections have been a major problem hindering wide industrial applications. Several methods have been proposed to improve the surface appearance of foams. In this study, we proposed a method to improve the surface appearance of polypropylene (PP) foams from the material property perspective, especially with regard to crystallization and viscosity. The basic idea of the surface improvement is to reduce the size of bubbles generated at the flow front, delay the solidification behavior of the polymer at the mold interface, squeeze the bubbles existing at the mold–polymer interface, and redissolve the bubbles into the polymer by holding pressure. Blending a low-modulus PP delays the crystallization of the polymers at the skin layer and solidification, taking enough time to squeeze the bubbles smaller. A sorbitol-based gelling agent, bis-O-([4 methylphenyl]methylene)-D-Glucitol, was used to increase the viscosity at a low strain rate to reduce the size of the bubbles generated at the flow front during the filling stage. The foam injection molding experiments demonstrated that the proposed method effectively improved the surface appearance of the foams. In particular, the surface appearance of the foams became almost equivalent to that of solid samples using low-modulus PP.     

Variation of internal structure and performance of polyethylene- and polypropylene-modified bitumen during blending process

Linear-viscoelastic characteristics and performance are evaluated throughout the blending process of polyethylene and polypropylene with bitumen. Results indicate that type, form and percentage of polyolefin play a significant role in the time evolution of the composite's mechanical response. Toluene extraction of modified bitumen revealed, for the first time, the formation of a sponge-like polymer network. Visual inspection and Fourier transform infrared analysis of the polyolefins recovered after extraction indicates higher affinity of the polyethylene with bitumen in agreement with the rheological test results. The use of polypropylene is discouraged if rutting performance is a concern, and polyethylene in both pellets and powder form at 4%, and after 210 min of blending produces a modified bitumen with acceptable performance.     

How the biaxially stretching mode influence dielectric and energy storage properties of polypropylene films

The most important polymer film used in commercial capacitors is biaxially oriented polypropylene (BOPP), which could be produced by sequentially or simultaneously biaxial orientation after the melt-extrusion. In order to disclose the influence of the stretching technique on the properties of films, the BOPP films with varied thickness were fabricated by sequential and simultaneous orientation, respectively. Compared to the sequentially biaxially stretched films, the crystal grains in the simultaneously biaxially stretched films are more isotropically dispersed. As temperature increases, all the BOPP films exhibit similar dielectric constant, and the simultaneous films have much lower dielectric loss thanks to the finer blended crystalline and amorphous phases. When the film thickness is smaller than 5 μm, the breakdown field strength, energy density and discharging time of the simultaneous films can be increased by at least 10% comparing to the sequential ones, which is very important for reducing the volume of the film capacitors. All the results suggest the simultaneously biaxial orientation mode shows significant advantages in producing thin BOPP films with better mechanical and electrical properties.     

1H T2‐NMR monitoring of crosslinked polyolefin aging

This work examines the correlation between the ¹H‐NMR T₂ relaxation constant and the mechanical properties of aged crosslinked polyolefin cable insulation. T₂ experiments on unswollen samples could not differentiate between unaged and highly aged materials; all exhibited ¹H T₂ constants of approximately 0.5 ms. To accentuate the effects of aging, samples were swollen in various solvents. Unaged samples had T₂ values of approximately 15 ms in good solvents. With thermal aging, T₂ values decreased as the ultimate tensile elongation decreased. However, the correlation between T₂ and elongation differed for samples irradiated with high‐energy radiation and for materials aged above versus below the crystalline melting temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2578–2582, 2003     

Some recent advances in polyolefin functionalization

Polyolefin‐based materials are increasingly being used in many industrial applications for packaging, automotive and construction materials. The recent developments of research have been aimed at making these materials, often complex, being mixtures, block copolymers, micro‐ and nanocomposites with inorganic and organic fillers, more efficient and environmentally friendly (through recycling processes, and the use of bio‐polyolefins). In this context, functionalized polyolefins, on the one hand, play a fundamental role in improving the morphology and thus the thermal and mechanical properties of heterophase systems, and, on the other hand, provide new materials difficult to obtain by conventional synthesis in connection with the type of inserted functionality. Therefore it appears to be of interest to report and discuss here the recent results concerning the radical grafting in the melt of different functionalities onto polyolefins as well as the capability reached of modulating ad hoc the degree of grafting and the final structure/architecture of functionalized polyolefins. © 2013 Society of Chemical Industry