Trans- and Dimethyl quinacridone nucleation of isotactic polypropylene

Isotaclic polypropylene (iPP) was nucleated specifically for structural and mechanical studies, especially of impact resistance. Nucleation was accomplished by two red pigments: a linear trans-quinacridone dye (as β-phase nucleator) and a dimethyl quinacridone resulting in the formalion of a pure α-phase structure. This procedure allowed the comparison of both the crystal structure and the morphology of the polymer. For the β-nucleated iPP, by means of the WAXS measurements in the transmission mode, a maximum of the k-value (fraction of β-phase) was found for a concentration of 5 × 10^?5 wt% of the trans-quinacridone. By means of polarized light microscopy (PLM), the mold temperature and pigment concentration dependent spherulites distribution on the cross section of the samples was observed. DSC permitted confirmation of the WAXS measurements, giving a characteristic double melting peak for the β polypropylene. By isothermal WAXS measurements the temperature of 135°C as the upper limit of the β phase was detected. For both nucleating agents (linear trans-quinacridone and dimethyl quinacridone) the dependence of the mechanical properties (modulus of elasticity and brittleness by impact resistance) on the pigment concentration was observed. For the β-phase iPP the highest ductility by impact testing corresponds to the highest values of the k parameter. The explanation is based on the SEM observations, which permitted the detection of spherulites with cross-hatched lamellae (for the α-spherulites) and with simple radial growth lamellae for the β-spherulites.     

Deformation behavior of isotactic polypropylene crystallized via a mesophase

The mechanical behavior of semicrystalline isotactic polypropylene (iPP) of different crystallinity, crystal morphology and superstructure was investigated by standard tensile stress–strain analysis, dynamic-mechanical analysis, and in situ observation of the deformation by atomic force microscopy (AFM). Emphasis is put on the comparison of the mechanical characteristics of specimens containing either non-isometric lamellae, being arranged in spherulites, or nodular isometric domains, which are not organized in a superstructure. The formation of lamellae/spherulites and of nodules was controlled by the conditions of crystallization. The replacement of cross-hatched monoclinic lamellae and a spherulitic superstructure by randomly arranged isometric nodules leads to a distinct increase of the ductility and toughness, even if the crystallinity is identical. The modulus of elasticity and the yield stress increase as expected with increasing crystallinity. Slightly lower values of Young’s modulus and yield strength are detected if samples contained non-lamellar crystals in a non-spherulitic superstructure, proving an effect of the crystal shape on the deformation behavior. For the first time, tensile deformation of semicrystalline iPP which contains nodular ordered domains instead of lamellae has been followed by in situ AFM.     

Influence of β nucleation on the mechanical properties of isotactic polypropylene and rubber modified isotactic polypropylene

The tensile and fracture behaviour of neat α and β nucleated isotactic polypropylene and rubber-modified α and β nucleated isotactic polypropylene has been investigated at test speeds of 0.0001-10 ms⁻¹ in the temperature range −30 to +60 °C. The presence of the β phase had little effect at low temperature. However, at +25 and +60 °C, it increased the speeds corresponding to the ductile-brittle transition in the neat polymer by more than three decades. This behaviour has been linked to changes in microdeformation mechanisms observed at the lamellar and spherulitic level, an increase in cavitational deformation in tensile tests and an increase in the strength of the β relaxation in dynamic mechanical spectra. In the blends, the presence of the β phase led to somewhat higher energy dissipation in regimes of ductile fracture. However, the ductile-brittle transitions were not significantly affected. The modifier phase was therefore inferred to control the initiation and propagation of the plastic zone ahead of the crack tip during fracture.     

Mesomorphic form of isotactic polypropylene in stereodefective polypropylene: Solid mesophase or liquid-crystal like structure

A study of the crystallization of the mesomorphic form of isotactic polypropylene (iPP) in samples of different stereoregularity prepared with metallocene catalysts is presented. Contrary to what claimed in the literature, we have found that the mesomorphic form can be obtained by quenching of the melt at 0 °C also in the case of low stereoregular samples, provided that the samples are kept at 0 °C for long time. The key is the formation of mesomorphic bundles with chains in ordered 3/1 helical conformation of size large enough to be stable and inhibit the crystallization of the α form at room temperature. For stereoirregular samples the concentration of long ordered helical stretches is low and this requires long residence time at 0 °C for the formation of mesomorphic aggregates of size larger than the critical size. This result provides evidence that the mesomorphic aggregates are not formed as a result of a cooperative process driven by entropy, as in the case of liquid crystals, but rather they form via a nucleation and growth mechanism, as in the normal crystallization processes, according to the idea that the mesophase of iPP is a highly defective crystalline form.     

Spherulite nucleation in blends of isotactic polypropylene with isotactic poly(butene-1)

The phase morphology and the influence of composition on the primary nucleation of isotactic polypropylene in isotactic polypropylene/isotactic poly(butene-1) (iPP/iPB) blends were investigated by electron and light microscopy and small-angle light scattering. It was found that iPP and iPB are miscible but the thermal treatment induces partial phase separation of components and the formation of iPP-rich and iPB-rich phases. The complete phase separation needs high temperatures and/or a long time of melt annealing. In samples crystallized isothermally at low undercooling the heterogeneous primary nucleation in blends is depressed as compared to plain iPP. In blends the less active heterogeneities lose their activity because of an increase of the energy barrier for critical size nucleus formation due to phase separation of blend components during crystallization. For the same reason the rate of homogeneous nucleation in blends decreases, as observed in samples crystallized at very high undercooling. At very high undercooling iPP and iPB are able to crystallize with similar rates, which results in the formation of a fraction of iPB spherulites in addition to iPP spherulites. Consequently the number of spherulites in the blend is larger than that in plain iPP, in spite of the decrease in the homogeneous nucleation rate of iPP in the blend. © 1994 John Wiley & Sons, Inc.     

Spherulite nucleation in isotactic polypropylene based nanocomposites with montmorillonite under shear

The crystallization of nanocomposites of isotactic polypropylenes with organo modified montmorillonite compatibilized by maleic anhydride grafted polypropylene was studied by light microscopy in isothermal conditions in quiescent state and in shear. The isothermal and nonisothermal crystallization of the composites was also investigated by DSC method. Only weak nucleation activity of montmorillonite was observed during crystallization in static conditions. The clay nucleation activity was greatly enhanced in shear-induced crystallization and resulted in a drastic decrease of spherulite sizes. In nanocomposite films crystallized isothermally the intense nucleation of isotactic polypropylene spherulites was observed when the polymer was forced to flow to compensate the volume shrinkage due to crystallization. It was also found that the presence of a glass support enhances spherulite nucleation in nanocomposites which is caused possibly by shear due to a difference in thermal shrinkage of a polymer matrix and a glass support.     

Primary nucleation behaviour in isotactic polypropylene/ethylene-propylene random copolymer blends

Primary nucleation of spherulites in blends of isotactic polypropylene (iPP) with ethylene-propylene random copolymer (EPM) has been investigated using optical microscopy. The number of spherulites generally increases with increasing EPM content. It is shown that this increase is caused by migration of heterogeneous nuclei across interface boundaries from EPM to iPP during melt-mixing. The migration was observed in the blends with the nucleating agent initially added to EPM before blending with iPP. It is suggested that the interfacial free energy difference between nuclei and the molten components of the blend is responsible for the migration of nuclei. It is also shown that self-seeded nucleation becomes damped in the blends due to partial solubility of the components and that the degradation of the blends during melt-annealing depresses the primary nucleation.     

Physical aging in isotactic polypropylene

Physical aging studies were made using commercial and laboratory samples of isotactic polypropylene. Linear and nonlinear viscoelastic responses were measured after quenching the glass from above the glass transition temperatures to below the glass transition. Results show that aging is not eliminated by large mechanical deformations; rather, the time required for the glass to age into equilibrium is independent of the applied stress. Results obtained are purely kinetic and interpreted as the effects accompanying the process of glass formation in a semicrystalline polymer. © 1996 John Wiley & Sons, Inc.     

SAXS study on structure formation from the uniaxially oriented glass in isotactic polypropylene

The structure formation of isotactic polypropylene from the uniaxially oriented glass into the smectic mesophase has been studied by small-angle X-ray scattering. Remarkable anisotropy between the directions parallel and perpendicular to the chain axis is found in the development of structure formation. Below −20 °C is observed a structure with density variation having the wave vector, perpendicular to the chain axis with a period of 5 to 6 nm. Between −20 and +25 °C, the density variations with both parallel and perpendicular to the chain axis develop. Above +25 °C, the density variation with perpendicular to the chain axis develops but disappears eventually, while that parallel to the chain axis keeps on growing.     

低等规聚丙烯的研制Ⅴ.粘性聚合物的分离技术

采用液相本体法生产的粘性低等规聚丙烯在排放输送和分离回收时易堵塞阀门和管道。模试结果表明：控制聚合时丙烯转化率为20％～50％,同时预先在闪蒸釜中加人表面分散剂质量分数约0．3％的液体介质及预先充人丙烯单体可以有效地解决这一问题。介绍了采用乙醇-水溶液作为分散介质的分离技术特征,并可用深度冷冻法或吸附极性分子法从回收体系中除去乙醇。     

Luminescence emission of isotactic polypropylene

In order to elucidate the origin of luminescent species in unstabilized commercial isotactic polypropylene (IPP), effects of hexane extraction and exposure of the extracted IPP film to the atmosphere on both fluorescence and phosphorescence emissions were examined. Fluorescence emission from the unextracted IPP film disappeared by the extraction, and only a very weak phosphorescence emission was found. During the exposure of the extracted IPP film to the atmosphere, both fluorescence and phosphorescence emissions appeared again. The intensity of the spectra increased with the exposure time and finally almost reached that from the unextracted IPP film. The results indicated that main fluorescent species in IPP are foreign impurities originating from an ambient atmosphere, and that contribution of a very minor amount of phosphorescence species such as carbonyl groups incorporated with the polymer was scarce.     

Preparation of isotactic polypropylene/polystyrene blends by diffusion and subsequent polymerization of styrene in isotactic polypropylene pellets

Isotactic polypropylene (iPP) pellets were used to prepare isotactic polypropylene/polystyrene (iPP/PS) blends by diffusion and subsequent polymerization of styrene in water medium, with initiator benzoyl peroxide (BPO) added after diffusion of styrene. Two methods, differencing in whether the excess monomer was removed after diffusion, were used and parameters influencing PS contents were investigated. Diffusion kinetic study showed that the diffusion coefficient at 90 °C is 2.8 times that at 80 °C due to the α relaxation of iPP segments. Investigation on the distribution state of styrene in the mixture before diffusion revealed that most styrene adsorbed on the surface of iPP pellets, and thus the diffusion behavior of styrene into iPP pellets in water medium is similar to that in bulk styrene. Phase morphology of a typical iPP/PS blend showed an average particle size of about 90 nm in the inner part of the iPP pellets. The diametrical distributions of PS showed that styrene can diffuse up to the center of the pellets at 90 °C. It is important to note that the depth of styrene is limited when the initiator BPO is added along with styrene, providing a good explanation for the previously reported ineffective solid-state modification of melt-extruded iPP pellets.     

Thermal characteristics and crystallinity of Ziegler–Natta isotactic polypropylene/metallocene isotactic polypropylene polyblended fibers

Ziegler–Natta isotactic polypropylene (ZN‐iPP) and metallocene isotactic polypropylene (m‐iPP) were extruded (in ratios of 75/25, 50/50, and 25/75) from one melt twin‐screw extruder to produce three ZN‐iPP/m‐iPP polyblended polymers and, subsequently, spin fibers. In this study, we examined the rheology of the ZN‐iPP/m‐iPP polyblended polymers and the thermal characteristics and crystallinity of the ZN‐iPP/m‐iPP polyblended fibers using gel permeation chromatography, rheometry, differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, density gradient analysis, and extension stress–strain measurement. The apparent melt viscosity of the ZN‐iPP/m‐iPP polyblended polymers revealed positive‐deviation blends. The 50/50 blend of ZN‐iPP/m‐iPP had the highest apparent melt viscosity. For five samples, the complex melt viscosity decreased with the angular frequency, which represented typical non‐Newtonian behavior. The Cole–Cole plot, which consisted of the imaginary part of the complex melt viscosity versus the real part of the complex melt viscosity plot, of the ZN‐iPP/m‐iPP polyblended polymers showed a semicircular relationship with the blend ratios. It indicated that the ZN‐iPP/m‐iPP polyblended polymers were miscible. We analyzed the shear modulus data (G′ vs G″) by plotting them on a log–log scale. The plot revealed almost the same slopes for the ZN‐iPP/m‐iPP polyblended polymers, which indicated a good miscibility between the ZN‐iPP and m‐iPP polymers. The experimental DSC results demonstrate that the ZN‐iPP and m‐iPP polymers constituted a miscible system. The crystallinity and tenacity of the ZN‐iPP/m‐iPP polyblended fibers initially increased and then fell as the m‐iPP content increased. Meanwhile, the 50/50 blend of ZN‐iPP/m‐iPP had the highest crystallinity and tenacity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology evolution including formation of cylindrulite in isotactic polypropylene derived from periodical shear field

It has been well established that periodical shear stress can improve the mechanical performance of isotactic polypropylene during injection molding. In the current study, Polarized Light Microscopy (PLM), two-dimensional Wide-Angle X-ray Diffraction (2D-WAXD), Scanning Electron Microscopy (SEM) were employed to investigate the morphology evolution of vibration sample. Compared with static sample, the morphology of vibration one, which is derived from periodical shear field, exhibits different hierarchy structure: there is an additional fiber layer containing cylindrulites between the shear layer and the core layer, and the orientation is enhanced obviously. Through etching technique, it is found that there exists non-crystalline component in the fibril (core) of cylindrulite, and it may induce the growth of β crystals directly regardless of its non-crystalline nature. Based on the investigated results, a model of formation of cylindrulite is proposed.     

Intrafibrillar bridging structures in strained isotactic polypropylene

The films made of isotactic polypropylene were strained up to 0.8 of their ultimate strain and subjected to isometric stress relaxation during 5 days. The strain-stress curves were measured at various stages of the sample treatment and the tangent moduli (E_t) of unstrained, as-strained and relaxed films were determined. The changes of values of E_t were put in comparison with the structural evolution of strained samples observed using the infrared and low-frequency Raman spectroscopic techniques. It was concluded that the three-dimensional intercrystallite bridges composed of straight-chain segments of lengths L_c<L<2L_c (L_c is the average thickness of crystallites) destruct as a result of chain-breaking process, but due to the chain-straightening events in isometrically relaxing samples, the intercrystallite space transforms to the rigid amorphous phase composed of ‘individual’ one-dimensional molecular stems.     

Character of crystallization nuclei in isotactic polypropylene

Examination of the isothermal crystallization and the effect of melting conditions on samples of isotactic polypropylene and its composite with talc, combined with electron-microscopic observation, has shown two types of heterogeneous nuclei effective in the crystallization process: (1) metastable nuclei, representing the unmelted crystalline phase of polypropylene, stabilized by solid heterogeneities, and operating after melting at relative low melting temperature and/or short melting time; and (2) stable crystallization nuclei, associated with solid heterogeneities, being probably catalyst residues. On the surface of these nuclei isotactic polypropylene tends to crystallize in an ordered fashion.     

聚丙烯复合材料的非等温结晶动力学

采用差示扫描量热仪研究了β成核剂和水滑石(LDH)/β成核剂复配的成核剂对聚丙烯(PP)非等温结晶动力学及熔融行为的影响。结果表明:加入成核剂后,PP中晶体分布不均匀且分散度增大。莫志深方法采用F(θ)表征聚合物在单位时间内达到某一结晶度时所需的冷却(或加热)速率,结晶度达到40%时,纯PP的F(θ)为3.82,加入β成核剂的PP的F(θ)为3.30,加入LDH/β成核剂的PP的F(θ)为2.49。与纯β成核剂相比,LDH/β成核剂能更好地提高PP的结晶温度、结晶速率,增强PP的β晶熔融峰,减弱β晶和α晶共存熔融峰和α晶熔融峰。     

固相氯化法氯化等规聚丙烯结构分析

借助ＤＳＣ,ＩＲ,＾１Ｈ－ＮＭＲ方法对搅拌式固相氯化制备的氯化等规聚丙烯的宏观氯原子分布和微观氯原子分布进行了分析。结果表明,搅拌式固相氯化法能够迅速破坏等规聚丙烯的结晶,从而得到宏观氯原子分布均匀的ＣＩＰＰ。此方法制备的ＣＩＰＰ主要为等丙烯分子链上的仲氢原子被取代的产物。     

The physical aging of isotactic polypropylene

The microstructural changes in isotactic polypropylene (PP), subsequent to quench from the melt to around T_g were studied using dynamic mechanical loss, volume dilatometry, small and wide angle X-ray scattering, infrared and NMR spectroscopy. The β-transition loss tangent and the specific volume decreased linearly with logarithm of aging time. Dynamic mechanical loss and NMR spectroscopy results established that amorphous chain mobility reduced during aging. X-ray and IR techniques showed that the crystallinity, the crystalline density, and the average chain conformation do not change during aging. Tensile tests indicated that diffusion of air or moisture into the polymer is not a competitive mechanism for the aging phenomenon. A simple free-volume model is quantitatively consistent with these observations. The fraction of the material which cannot age increased as the quench temperature decreased. Further, at lower temperatures a portion of the nonageable fraction is shown to reside in the amorphous fraction.