TEXTURE AND CRYSTALLINITY EVOLUTION IN ISOTACTIC POLYPROPYLENE INDUCED BY ROLLING AND THEIR INFLUENCE ON MECHANICAL PROPERTIES

The orientation and crystallinity evolution of isotactic polypropylene （iPP） induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isotactic polypropylene sheets were also measured in this work. The texture component method was used to analyze the rolling texture. The rolling texture consists mainly of （010）[001], （130）[001] and [001]//RD fiber components in the sample with a rolling true strain of 1.5. The results reveal that crystallinity drastically decreases during rolling. It is suggested that amorphization is a deformation mechanism which takes place as an alternative to crystallographic intralamellar slip depending on the orientation of the lamellae. Both the orientation and crystallinity affect the tensile mechanical properties of rolled polypropylene. Crystallinity influences the elastic modulus on both directions and yield strength on transverse direction at the first stage of deformation. Orientation is the main reason for the changes of mechanical properties, especially at the latter part of deformation. The changes of both tensile strength and elongation percentage on rolling direction are larger than those on transverse direction, which results from the orientation. At last, the anisotropic mechanical properties occur on the rolling and transverse direction： high tensile strength with low elongation percentage on rolling direction and low tensile strength with high elongation percentage on transverse direction.

PARTIAL MELTING AND RECRYSTALLIZATION OF ISOTACTIC POLYPROPYLENE

A relatively high predetermined crystallization temperature （135℃） was chosen to grow well developed iPP spherulites, then the partial melting was carried out at a temperature of 165℃, where the preformed spherulites were seen to only decrease their size but not completely melted. The crystallization behavior of partially melted isotactic polypropylene （iPP） has been carefully examined by different scanning calorimetry （DSC） and polarized light microscopy （PLM）. The experimental results show that at a special annealing temperature （165℃） the melting behavior of iPP includes two parts with different mechanism, one part is the melting of iPP spherulite outside, another is the partial lamellae perfection during longer annealing time in the unmelted spherulite. The conformational orders of the iPP melt decrease with the increase of the annealing temperature.

Vibration-dependent Crystal Form of Isotactic Polypropylene under Nonisothermal Crystallization

A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibration treatment were investigated by means of differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The results reveal that the crystallinity of the vibrated samples decreases at a high cooling rate, but it remains constant at a low cooling rate because of the chain relaxation of iPP. It has been found that vibration obviously increases the content of β-form of crystal phase and the amount of β-crystal mainly depends on the vibration amplitude.

Determination and Temperature Dependence of Plateau Modulus for Polymerization of Propylene to Isotactic Polypropylene with Ultra-high Molecular Weight under Catalysis of Ziegler-Natta Catalyst

The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G″) plots at 180 and 200 ℃ versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0.01-100 rad/s for Ziegler-Natta catalyzing ethylene-propylene random copolymerization(PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G″(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus(G 0_N) of UHPPH from a certain experimental temperature G″(ω) curve directly. For UHPPH, the G 0_N determined to be 4.28×10 5 and 3.62×10 5 Pa at 180 and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G 0_N has no relation to the molecular weight.

EPITAXIAL CRYSTALLIZATION OF POLY(ε-CAPROLACTONE)ON HIGHLY ORIENTED ISOTACTIC POLYPROPYLENE

Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright field(BF)electron micrograph and electron diffraction indicate that the PCL can epitaxially grow on iPP substrate and form cross-hatched lamellar texture.The c axes of PCL are ±500 apart from the c axes of iPP. The contact planes of the two kinds of crystals are(010)of iPP and(100) of PCL,respectively.

PREPARATION AND MORPHOLOGY OF ISOTACTIC POLYPROPYLENE WITH HIGH CONTENT OF β CRYSTALLINE FORM

Isotactic polypropylene (iPP) with high content of ~ crystalline form was prepared by adding a series of new p form nucleators. The spherulites and morphology of//farm iPP (//-iPP) were investigated by wide-angle X-ray diffraction(WAXD), polarizing microscope (PLM), scanning electron microscope (SEM) and small-angle light scattering (SALS). WAXD experimental results indicate that the amount of p form in iPP (K_x) increases with increasing /~ nucleator content from zero to 0.07 wt% or crystallization temperature T_c from 20 to 120℃ and that the highest K_x value is up to 0.95. PLM observations suggest that p spherulites exhibit bright color and that their Maltese Crosses display some concentric banding of a rather spiky, jagged character. Their !amellae are smooth and relaxed layer-plate like structure by SEM and their SALS H_v patterns arc four-petalled.

The Synthesis of Isotactic Polypropylene with Spherical Morphology via Supported Metallocene Catalyst

Polymerization of propylene was carried out under bulk process at 70 degrees C using the supported metallocene catalyst with four kinds of SiO2 as carrier with triethylaluminum used as cocatalyst. The morphology of the products was studied by SEM. It was found the property of the carriers gave great effect on the fine structure of the products as well as the apperance.

Changes of crystallinity and spherulite morphology in isotactic polypropylene after rolling and heat treatment

The spherulite morphology of the rolled and subsequent heat-treated isotactic polypropylene （iPP） was observed by polarized microscopy, and the crystallinity evolution of materials was also measured by the wide angle X-ray scattering （WAXS）. Rolling led to the oblate spherulites in the deformed iPP samples. The sheared crystalline lamellae broke apart into sets of crystalline blocks during rolling. As a result, the crystallinity of the iPP samples was greatly reduced during deformation, which induced the unclear spherulites and spherulite boundaries. Subsequent heat treatment resulted in the strong reerystallization of the rolled iPP samples. But the recrystaUizatinn in this work only meant the rearrangement of the macromolecule along the unbroken crystalline lamellae and the existing small crystalline blocks in the deformed spherulites. Heat treatment did not change the shape of the spherulites formed during deformation. The recrystallization also resulted in very clear spherulites and spherulite boundaries.

Characterization of Isotactic Polypropylene/Talc Composites Prepared by Extrusion Cum Compression Molding Technique

Extrusion-Compression molded isotactic polypropylene (iPP) composites containing 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% of talc filler were studied by scanning electron microscopy (SEM), simultaneous thermal analysis (STA) and physical testing. The scanning electron microscope (SEM) micrographs of neat iPP and composites with 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% talc content show that neat PP, 10 wt%, 20 wt%, and 30wt% talc composites surface is smooth in comparison to 40 wt% and 50 wt% talc composites. It is also observed that talc is dispersed uniformly in the matrix and this uniform dispersion is not decreased even with talc content as high as 30 wt% talc. The composites of 40 wt% and 50 wt% talc contain more crack, agglomerates or larger particles. Bulk density of the composites decreases with the increase of talc content. With the increase of percentage of talc and period of immersion, the water absorption (WA) increases. Thermal analyses indicate a considerable increase of thermal stability of the composites with filler addition.

iPP/nano-CaCO3/PP-g-GMA复合材料的制备与性能

以等规聚丙烯(iPP)、纳米碳酸钙(nano-CaCO_(3))和甲基丙烯酸缩水甘油酯接枝改性抗冲共聚聚丙烯(PP-g-GMA)为原料,通过熔融共混法制备了iPP/nano-CaCO_(3)/PP-g-GMA复合材料。研究了PP-g-GMA对iPP/nano-CaCO_(3)/PP-g-GMA复合材料力学性能、结晶行为和微观结构的影响,并分析了其增韧机理。结果表明:PP-g-GMA和nano-CaCO_(3)具有协同增韧作用,当两者用量均为40.0质量份时,iPP/nano-CaCO_(3)/PP-g-GMA复合材料23℃时的冲击强度约为纯iPP的6.9倍。PP-g-GMA和nano-CaCO_(3)均具有成核作用,促使基体球晶细化。PP-g-GMA中的橡胶相以球形海岛形式分散在iPP中,起到增韧作用。

Significantly Enhanced Melt Memory Effect of Metallocene-made Isotactic Polypropylene Containing Talc

The melt memory effect is a widely observed phenomenon in semi-crystalline polymers. In practical applications, various additives are usually introduced into polymers, which may affect their melt memory behavior. In this work, the effect of talc on the melt memory effect of metallocene-made isotactic polypropylene(M-PP) was investigated in detail by using the differential scanning calorimetry. The results indicated that the introduction of talc significantly strengthened the melt memory effect of M-PP. Specifically, the upper limit temperature of Domain II increased from 161 ℃ to 174 ℃, resulting in a substantial widening of the temperature range of Domain IIa from 1 ℃ to 14 ℃. Analysis of the crystal orientation of the M-PP containing talc cooled from various Ts suggested that the remarkably enhanced melt memory effect could be ascribed to the stabilization of oriented nuclei facilitated by talc. This stabilizing effect was likely attributable to the prefreezing effect or the sorption interaction between talc and the M-PP chains.

丙烯等规配位聚合催化剂及电容器膜基材iPP的制备技术研究进展

生产包括电容器膜基材iPP在内高端聚丙烯的关键技术是丙烯高等规聚合的高活性催化剂和先进聚合工艺。本文详细介绍了丙烯聚合催化剂的发展历程,包括高效Ziegler-Natta催化剂、茂金属催化剂和非茂金属催化剂,指出了在合成电容器基材iPP方面此三类催化剂的优缺点。阐述了烯烃聚合催化剂的近期发展动态:产生了在催化剂结构/组成中引入强吸电子基团有利于提高催化剂活性和聚烯烃分子量的新理论,发展了新一代烯烃聚合催化剂包括内外给电子体于同一分子的丙烯聚合催化剂和全杂环金属有机催化剂,提出了制备嵌端共聚烯烃的可逆“络合-断开”配位聚合新方法。基于丙烯聚合先进工艺,结合高端电容器膜基材iPP技术指标的严苛要求,分析了聚丙烯粉料和粒料中灰分产生的主要因素,建立了在聚丙烯粉料灭活之前进入复合有机溶剂洗涤工序的生产方法,制备合格的高端电容器膜基材i PP。

High Efficieney Synthesis of Isotaetie Polypropylene and Linear Polyethylene Using a New C_2-symmetric Carbon-bridged Zirconocene Catalyst

Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic polypropylene （PP） was obtained with the highest activity of 6.37× 107g PP （molZr）^-1h^-1. The mesomeso （mmmmm） pentads sequence content of PP was determined by 13C NMR spectroscopy. The dependence of the microstructure on the reaction temperature and the AI/Zr molar ratio was examined and the catalytic activity of complex 5 was compared with that of the similar ansa-zirconocene 3. The high activity of the new zirconocene 5 for propylene isospectic polymerization at high temperature （60℃） is the result of its unique bridged-group structure. Complex 5/MAO displays also high catalytic activity of 0.46× 10^6 to 9.87× 10^6g PE（molZr）^-h^-in the homo-polymerization of ethylene, The visometric molecular weight of PE ranges from 0.97×10^4 to 11.16×10^4 g.mol^- under the given conditions.^13C NMR spectroscopy analysis proves the PE to be linear polyethylene （LPE）.

Experiment and simulation of foaming injection molding of polypropylene/nano-calcium carbonate composites by supercritical carbon dioxide

Microcellular injection molding of neat isotactic polypropylene(iPP) and isotactic polypropylene/nano-calcium carbonate composites(i PP/nano-CaCO_3) was performed using supercritical carbon dioxide as the physical blowing agent. The influences of filler content and operating conditions on microstructure morphology of i PP and i PP/nano-CaCO_3 microcellular samples were studied systematically. The results showed the bubble size of the microcellular samples could be effectively decreased while the cell density increased for i PP/nano-CaCO_3 composites, especially at high CO_2 concentration and back pressure, low mold temperature and injection speed, and high filler content. Then Moldex 3D was applied to simulate the microcellular injection molding process, with the application of the measured ScCO_2 solubility and diffusion data for i PP and i PP/nano-Ca CO_3 composites respectively. For neat i PP, the simulated bubble size and density distribution in the center section of tensile bars showed a good agreement with the experimental values. However, for i PP/nano-CaCO_3 composites, the correction factor for nucleation activation energy F and the pre-exponential factor of nucleation rate f_0 were obtained by nonlinear regression on the experimental bubble size and density distribution. The parameters F and f_0 can be used to predict the microcellular injection molding process for i PP/nano-CaCO_3 composites by Moldex 3D.

Preparation of Ultra-High Molecular Weight Polypropylene Using Ziegler-Natta Catalyst via Combining Internal Electron Donor and Cocatalyst Loading

Due to the development of the new energy industry,polypropylene with ultra-high molecular weight plays a crucial role for battery isolation membrane.This work investigated the effect of internal electron donor of Ziegler-Natta catalyst system on the molecular weight of the obtained polypropylene.The scanning electron microscope(SEM)and Canon camera were used to characterize the surface morphologies of catalyst particles and polymer particles,respectively.Compared with the polypropylene particles featuring a spherical shape,these study results confirmed that the morphology duplication theory from the catalyst particle to the morphology of polymer particle was exhibited.The gel permeation chromatography(GPC)results revealed that the obtained polypropylene has a much higher average molecular weight than those prepared by conventional method.The Fourier transform infrared spectrometry(FT-IR)and X-ray photoelectron spectroscopy(XPS)revealed that the carbonyl oxygen atom on ester group was preferentially bound to Mg and Ti,as compared to the ether oxygen atom.The XPS results showed that the ratio of Ti^(3+)/Ti^(4+)could be changed by internal electron donors.When Ti3+content was nearly 99%in the Ziegler-Natta catalyst system,isotactic polypropylene with an ultra-high molecular weight of up to 1.42×10^(6)g/mol was obtained by Cat.3.This result implied that internal electron donor ID3 could reduce theβ-hydride elimination reaction to further increase the molecular weight of the obtained polymer.

HCSW/iPP复合材料性能及诱导β晶的机理研究

将质量分数20%半水硫酸钙晶须(HCSW)与等规聚丙烯(iPP)熔融挤出后制备了HCSW/iPP复合材料,研究了HCSW/iPP复合材料性能以及HCSW对iPP诱导β晶的机理。结果表明:HCSW对iPPβ晶有良好的成核效果;与iPP相比,HCSW/iPP复合材料的力学性能有不同程度提高;利用“晶格匹配理论”计算得出HCSW与iPP有较好的附生效果。

Direct Synthesis of Ultrahigh Molecular Weight Functionalized Isotactic Polypropylene

Ultrahigh molecular weight functionalized isotactic polypropylene(f-UHMW-iPP)through the direct copolymerization of propylene with polar monomers is highly desirable but has not been accessed thus far because it involves challenging regio-and stereochemistry along with usually reduced molecular weight.Herein,in contrast to the unsuccessful catalyst strategy,a polar monomer-assisted strategy is used to access the above material.The introduction of O-or S-functionalized long-chain polar olefins into the hafnium-catalyzed copolymerization of propylene(and bulkierα-olefins)significantly increases the copolymer molecular weight with a maximum observed increase of+488%.f-UHMW-iPP and functionalized isotactic poly(α-olefin)s(M_(w)>2000 kDa,[mmmm]:99%)are thus prepared at ambient conditions.The incorporation of 1 mol%of polar monomer improves the surface property and significantly increases the long-sought toughness(860%)of brittle iPP,without reducing the tensile strength(42 MPa)due to the key achievement of ultrahigh molecular weight.A discussion of the mechanism involved in the beneficial effects of incorporating the polar monomer is herein presented by an in-depth density functional theory calculation.

CRYSTALLIZATION BEHAVIOR AND MORPHOLOGY OF ONE-STEP REACTION COMPATIBILIZED MICROFIBRILLAR REINFORCED ISOTACTIC POLYPROPYLENE/POLY(ETHYLENE TEREPHTHALATE)(iPP/PET) BLENDS

One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of CMRB were systematically investigated. Scanning electronic microscopy （SEM） observations showed blurry interface of compatibilized common blend （CCB）. The crystallization behavior of neat iPP, CCB, microfibrillar reinforced iPP/PET blend （MRB） and CMRB was investigated by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The increase of crystallization temperature and crystallization rate during nonisothermal crystallization process indicated both PET particles and mierofibrils could serve as nucleating agents and PET microfibrils exhibited higher heterogeneous nucleation ability, which were also vividly revealed by results of POM. Compared with MRB sample, CMRB sample has lower crystallization temperature due to existence of PET microfibrils with smaller aspect ratio and wider distribution. In addition, since in situ compatibilizer tends to stay in the interphase, it could also hinder the diffusion ofiPP molecules to the surface of PET phase, leading to decrease of crystallization rate. Two-dimensional wide-angle X-ray diffi：action （2D-WAXD） was preformed to characterize the crystalline structure of the samples by injection molding, and it was found that well-developed PET microfibrils contained in MRB sample promoted formation of t-phase of/PP.

TIPS法iPP中空纤维膜的拉伸性能研究

通过熔融共混等规聚丙烯(iPP)/邻苯二甲酸二丁酯(DBP)/邻苯二甲酸二辛酯(DOP)体系,采用热致相分离法(TIPS)制备iPP中空纤维膜,且在不同的拉伸温度及拉伸比下对中空纤维膜进行拉伸研究.对膜结构与透过性能进行了表征.采用环境扫描电子显微镜(SEM)对膜的内、外表面以及截面结构进行观测,发现拉伸后膜外表面的皮层以及膜结构得到有效改善.使用电子式万能试验机对中空纤维膜的拉伸强度进行了测试.随着拉伸温度和拉伸比的增加,膜的孔隙率、纯水通量以及拉伸强度均呈现先增大后减小的趋势.膜的孔隙率最大可提高35.3%,纯水通量提高了286.9%,拉伸强度可提高至6.86 MPa.nano-SiO2(纳米SiO2)添加的杂化膜经过拉伸后,孔隙率增大了46.8%,纯水通量提高了416.1%,拉伸强度提高了181.9%.研究表明:通过对iPP中空纤维膜进行拉伸处理,可以优化膜结构,并改善了膜表面皮层以及透过性能.

等规度和分子量及其分布对聚丙烯结晶行为及力学性能的影响

选取了3种具有不同等规度和不同分子量及其分布的均聚聚丙烯试样,利用DSC,GPC,SAXS,WAXD等方法研究了等规度、分子量及其分布对均聚聚丙烯结晶行为及力学性能的影响。实验结果表明,结晶行为主要受试样等规度的影响,对于等规度相近的试样,结晶温度和结晶度还受试样分子量及其分布的影响;力学性能与结晶度呈正相关,高等规度、宽分子量分布的试样具有更高的结晶度,以及较高的屈服应力、弯曲模量和热变形温度。