无规共聚PP与嵌段共聚PP共混的研究

用IR、DSC、SEM和力学性能测试方法研究了一种无规共聚PP（PP-R）和一种嵌段共聚PP（PP-B）及其共混物的结构与性能。结果表明,PP-R和PP-B都能结晶,但PP-B结晶较慢、结晶度较低;PP-R不含而PP-B含有呈球粒状分散的乙丙橡胶（EPR）相和乙烯嵌段（PE）相;随共混物中PP-B含量增加,常温和低温冲击韧性显著提高,力学强度在略有下降后能持平或回升,这些性能变化是上述PP-R、PP-B结构特点的一种综合效应。     

抗冲聚丙烯结构与性能研究

对部分国内外抗冲聚丙烯(PP)产品进行了微观形态和结构分析，研究其对材料宏观力学性能的影响。实验结果表明：抗冲PP是一个含有PP均聚物、丙烯与乙烯-丙烯两嵌段共聚物、乙丙橡胶(EPR)、聚乙烯均聚物等的多相体系。EPR的分子序列结构对聚合物抗冲击性能起主要作用。在序列结构中，丙烯、乙烯单体在分子链上的位置交换越频繁，抗冲击性能越得到提高。丙烯序列平均长度的增大对抗冲击性能有一定的削弱作用。     

EPR@PP聚丙烯基直流绝缘材料的制备及其性能研究

聚丙烯基绝缘材料具有优异力学性能和电学性能,常被使用在高压直流电输送领域。通过两段共聚的方法合成了不同橡胶相（EPR）含量的EPR@PP共聚物绝缘材料,考察共聚物的形貌与结构、热学性能、力学性能以及电学性能。结果表明：共聚物中含有乙丙二元无规聚合物结构,归属于EPR橡胶相结构。EPR均匀镶嵌在PP基体中形成“海岛”结构,平均粒径为1.31μm。共聚物的结晶度比均聚PP低,但仍为α晶型。二甲苯可溶物结果显示,EPR的含量随着乙丙比的增加而增加。共聚物的热变形温度最高可达107.42℃,低于均聚PP。共聚物熔融温度与结晶温度较高,说明共聚物适用于高温环境。与均聚PP相比,随着EPR含量的增加,共聚物常温和低温悬臂梁冲击强度大幅度增加,拉伸强度、断裂强度、弯曲模量总体保持较高水平,说明共聚物具有良好的力学性能。引入适当的EPR可以提高PP的介电常数、体积电阻率以及击穿强度,减小介电损耗,改善聚丙烯基材料的绝缘性能。     

SSA热分级技术在表征IPC各组分相互作用中的应用

对典型抗冲共聚聚丙烯(IPC)进行了溶剂分级,分级出三组分,即乙烯-丙烯无规共聚物(EPR)、乙烯-丙烯嵌段共聚物(EbP)、丙烯均聚物(PPH)。通过连续自成核与退火(SSA)热分级技术分析了IPC,EbP/EPR,EbP/PPH二元非共混物和溶液共混物的结晶行为。采用扫描电子显微镜观察了PPH/EPR二元、PPH/EPR/EbP三元溶液共混物的冲击断面。结果表明:SSA热分级技术对分析IPC及其分级出的各级分的异质性具有较好的分辨效果;EbP和PPH组分易形成共晶,而EPR对EbP的结晶起到了稀释和弱化作用,从而证明EbP和PPH,EbP和EPR之间均存在相互作用;PPH/EPR溶液共混物中加入EbP后,冲击断面出现韧性断裂,说明EbP起到了增容PPH基体和分散相EPR的作用。     

提高嵌段共聚PP冲击强度的措施探讨

介绍了生产嵌段共聚聚丙烯(PP)的工艺和改善冲击强度的机理,分析了影响嵌段共聚PP冲击强度的主要因素：二聚物的含量、结构及其特性粘数;提出了3条提高嵌段共聚PP冲击强度的措施：提高嵌段共聚PP的键合乙烯量、降低气相比以及控制二聚物特性粘数在适当的范围。     

新型聚烯烃弹性体OBC增韧共聚PP的研究

进行乙烯-辛烯嵌段型共聚物(OBC)共混改性共聚级聚丙烯(Co-PP)的研究,考察了共混物的冲击强度、拉伸强度、断裂伸长率、熔体流动指数、维卡软化点等机械物理性能和冲击断面形貌,进行了动态力学分析,并与Co-PP/乙烯-辛烯无规共聚物(POE)、Co-PP/乙烯-丁烯共聚物(EBC)共混体系比较。结果表明,弹性体含量达到10%(wt)时,三种共混体系均已基本实现"脆韧转变",含较长支链的OBC与POE对Co-PP有更好的增韧效果;低温下,Co-PP/OBC的抗冲性能尤佳,其低温内耗峰温度低、储能模量高。OBC大分子链中PE嵌段的存在,使其自身及其与Co-PP共混物的加工与耐热性均明显优于其它两种弹性体。     

世界主要塑料期刊文献摘要⑨

国际现代塑料(美国) Modern Plastics International 10月号(1990) ☆无规共聚PP用途更广(p46) 以乙烯和丁烯—1、己烯—1为共聚单体的聚丙烯无规共聚物,透明度和冲击强度优于聚丙烯均聚物。其中,多元共聚物热封性能好,而且几乎无臭气迁移,期待着它在食品容器的应用。本文介绍多种无规共聚PP及其特性以及在注射拉伸吹塑成型上的应用。☆等离子技术的进步扩大了表面处理的选择     

抗冲聚丙烯管材专用树脂的结构与性能

研究了乙丙嵌段共聚聚丙烯(PP-B)管材专用树脂的结构与性能。PP-B具有典型的乙丙嵌段共聚物序列结构,是含有丙烯均聚物(PP-H)、乙丙橡胶(EPR)及可结晶乙丙共聚物的抗冲聚丙烯(PP);其中,均聚物与共聚物比例合理,形成的EPR多、粒径小,对提高冲击强度有利。提高PP-H的质量分数和等规指数,可有效提高PP- B的刚性。PP-B的熔点与PP-H近似;相对分子质量分布较宽,流变性能好;微观与亚微观结构合理,宏观性能优良。     

CW169冷热水输送管道系统用的聚丙烯原料

聚丙烯管道系统可选用(1)PP-H(均聚PP),(2)PP-R(无规共聚PP),它是丙烯与另一种烯烃共聚成的无规共聚物,(3)PP-B(嵌段共聚PP),由PP-H或PP-R与橡胶形成两相或多相丙烯共聚物,是一种耐冲击性聚丙烯。PP-R与PP-B的简单区分法,用DSC法测它们的熔点时PP-R为142℃左右而PP-B大于160℃。     

不同化学结构的PP对热塑性弹性体复合材料性能的影响

研究了不同化学结构的聚丙烯(PP)对苯乙烯-乙烯/丁烯-苯乙烯共聚物(SEBS)/白油/PP热塑性弹性体复合材料力学性能和流动性能的影响。结果表明,复合材料的力学性能与所添加PP的力学性能保持一致,按照均聚PP、无规共聚PP、共聚PP的化学结构特性,复合材料的拉伸性能、弯曲性能和硬度都依次变小;但是复合材料的流动性能不仅和PP的熔体质量流动速率(MFR)有关系,而且还与PP和SEBS的相互作用有关。在PP的MFR相同的情况下,复合材料的MFR按照均聚PP、无规共聚PP、共聚PP的不同依次降低。     

The Use of Ethylene/Propylene Copolymers as Compatibilizers for Recycled Polyolefin Blends

Compatibilizing effects of ethylene/propylene (EPR) diblock copolymers on the morphology and mechanical properties of immiscible blends produced from recycled low‐density polyethylene (PE‐LD) and high‐density polyethylene (PE‐HD) with 20 wt.‐% of recycled poly(propylene) (PP) were investigated. Two different EPR block copolymers which differ in ethylene monomer unit content were applied to act as interfacial agents. The morphology of the studied blends was observed by scanning‐ (SEM) and transmission electron microscopy (TEM). It was found that both EPR copolymers were efficient in reducing the size of the dispersed phase and improving adhesion between PE and PP phases. Addition of 10 wt.‐% of EPR caused the formation of the interfacial layer surrounding dispersed PP particles with the occurrence of PE‐LD lamellae interpenetration into the layer. Tensile properties (elongation at yield, yield stress, elongation at break, Young's modulus) and notched impact strength were measured as a function of blend composition and chemical structure of EPR. It was found that the EPR with a higher content of ethylene monomer units was a more efficient compatibilizer, especially for the modification of PE‐LD/PP 80/20 blend. Notched impact strength and ductility were greatly improved due to the morphological changes and increased interfacial adhesion as a result of the EPR localization between the phases. No significant improvements of mechanical properties for recycled PE‐HD/PP 80/20 blend were observed by the addition of selected block copolymers.     

Mechanical properties and morphology of crosslinked PP/PE blends and PP/PE/propylene–ethylene copolymer blends

Blending is an effective method for improving polymer properties. However, the problem of phase separation often occurs due to incompatibility of homopolymers, which deteriorates the physical properties of polyblends. In this study, isotactic polypropylene was blended with low-density polyethylene. Crosslinking agent and copolymers of propylene and ethylene (either random copolymer or block copolymer) were added to improve the interfacial adhesion of PP/LDPE blends. The tensile strength, heat deflection temperature, and impact strength of these modified PP/PE blends were investigated. The microstructures of polyblends have been studied to interpret the mechanical behavior through dynamic viscoelasticity, wide-angle X-ray diffraction, differential scanning calorimetry, picnometry, and scanning electron microscopy. The properties of crosslinked PP/PE blends were determined by the content of crosslinking agent and processing method. For the material blended by roll, a 2% concentration of peroxide corresponded to a maximum tensile strength and minimum impact strength. However, the mechanical strength of those products blended by extrusion monotonously decreased with increasing peroxide content because of serious degradation. The interfacial adhesion of PP/PE blends could be enhanced by adding random or block copolymer of propylene and ethylene, and the impact strength as well as ductility were greatly improved. Experimental data showed that the impact strength of PP/LDPE/random copolymer ternary blend could reach as high as 33.3 kg · cm/cm; however, its rigidity and tensile strength were inferior to those of PP/LDPE/block copolymer blend.     

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene (hiPP) were studied by solvent extraction fractionation, transmission electron microscopy (TEM), selected area electron diffraction (SAED), nuclear magnetic resonance (¹³C‐NMR), and selected reblending of different fractions of hiPP. The results indicate that hiPP contains, in addition to polypropylene (PP) and amorphous ethylene‐propylene random copolymer (EPR) as well as a small amount of polyethylene (PE), a series of crystallizable ethylene‐propylene copolymers. The crystallizable ethylene‐propylene copolymers can be further divided into ethylene‐propylene segmented copolymer (PE‐s‐PP) with a short sequence length of PE and PP segments, and ethylene‐propylene block copolymer (PE‐b‐PP) with a long sequence length of PE and PP blocks. PE‐s‐PP and PE‐b‐PP participate differently in the formation of multilayered core‐shell structure of the dispersed phase in hiPP. PE‐s‐PP (like PE) constructs inner core, PE‐b‐PP forms outer shell, while intermediate layer is resulted from EPR. The main reason of the different functions of the crystallizable ethylene‐propylene copolymers is due to their different compatibility with the PP matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of copolymerization conditions on the structure and properties of polyethylene/polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys synthesized in gas‐phase with spherical ziegler‐natta catalyst

A spherical TiCl₄/MgCl₂‐based catalyst was used in the synthesis of polyethylene/polypropylene/poly (ethylene‐co‐propylene) in‐reactor alloys by sequential homopolymerization of ethylene, homopolymerization of propylene, and copolymerization of ethylene and propylene in gas‐phase. Different conditions in the third stage, such as the pressure of ethylene–propylene mixture and the feed ratio of ethylene, were investigated, and their influences on the compositions, structural distribution and properties of the in‐reactor alloys were studied. Increasing the feed ratio of ethylene is favorable for forming random ethylene–propylene copolymer and segmented ethylene–propylene copolymer, however, slightly influences the formation of ethylene‐b‐propylene block copolymer and homopolyethylene. Raising the pressure of ethylene–propylene mixture results in the increment of segmented ethylene–propylene copolymer, ethylene‐b‐propylene block copolymer, and PE fractions, but exerts a slight influence on both the random copolymer and PP fractions. The impact strength of PE/PP/EPR in‐reactor alloys can be markedly improved by increasing the feed ratio of ethylene in the ethylene–propylene mixture or increasing the pressure of ethylene–propylene mixture. However, the flexural modulus decreases as the feed ratio of ethylene in the ethylene–propylene mixture or the pressure of ethylene–propylene mixture increases. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2481–2487, 2006     

Toughening and reinforcing of polypropylene

To improve the mechanical properties of polypropylene (PP), some elastomers and fillers are used. The impact properties and tensile strength are affected by both the mineral additives and the polymer additives. There are also some changes in the thermal properties. To improve the interfacial adhesion, some low molecular polymers are added to assist the dispersion of the fillers and the uniformity of the various polymers with PP. The addition of low-density polyethylene (LDPE), high-density polyethylene (HDPE), or the styrene–butylene–styrene block copolymer (SBS) can improve the impact properties of PP. The propylene–ethylene copolymer has a more pronounced effect than does the physical blending of PP with PE. Calcium carbonate can reinforce PP resin. The ethylene–vinyl acetate copolymer (EVA) has an effect on the printing properties of the PP. © 1996 John Wiley & Sons, Inc.     

Dynamic mechanical properties and morphology of polypropylene block copolymers and polypropylene/elastomer blends

The relation between the dynamic mechanical properties and the morphology of polypropylene (PP) block copolymers and polypropylene/elastomer blends was studied by dynamic mechanical analysis (DMA), light- and electron microscopy. The latter techniques contributed to an improvement in assignments of relaxation transitions in the DMA spectra. It was established that PP block copolymers had multiphase structure since the ethylene/propylene rubber phase (EPR) formed in the copolymerization contained polyethylene (PE) domains. An identical morphology was found in the case of PP/polyolefin thermoplastic rubber (TPO) blends. Impact modification of PP by styrene/butadiene block copolymers led to a multiphase structure, too, due to the polystyrene (PS) domains aggregated in the soft rubbery polybutadiene phase. In the semicrystalline polyolefinic and in the amorphous styrene/butadienebased thermoplastic rubbers, PE crystallites and PS do mains acted as nodes of the physical network structure, respectively. PP/EPDM/TPO ternary blends developed for replacing high-density PE showed very high dispersion of the modifiers as compared to that of PP block copolymers. This fine dispersion of the impact modifier is a basic regulating factor of impact energy dissipation in the form of shear yielding and crazing.     

Effect of the structure on the morphology and spherulitic growth kinetics of polyolefin in‐reactor alloys

Four polyolefin in‐reactor alloys with different compositions and structures were prepared by sequential polymerization. All the alloys were fractionated into five fractions: a random copolymer of ethylene and propylene (25°C fraction), an ethylene–propylene segmented copolymer (90°C fraction), an ethylene homopolymer (110°C fraction), an ethylene–propylene block copolymer (120°C fraction), and a propylene homopolymer plus a minor ethylene homopolymer of high molecular weight (>120°C fraction). The effect of the structure on the morphology and spherulitic growth kinetics of the polypropylene (PP) component in the alloys was investigated. The polyolefin alloys containing a suitable block copolymer fraction and a larger amount of PP had a more homogeneous morphology, and the crystalline particles were smaller. Quenching the polyolefin alloys led to smaller crystallites and a more homogeneous morphology as well. Isothermal crystallization was carried out above the melting temperature of polyethylene, and the growth of PP spherulites was monitored with polarized optical microscopy with a hot stage. The alloys with higher propylene contents exhibited a faster spherulitic growth rate. The fold surface free energy was derived, and it was found that a large amount of block copolymer fractions and random copolymer fractions could reduce the fold surface free energy. The structure of the alloys also affected the crystallization regime of PP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 632–638, 2005     

Preparation and characterization of high MFR polypropylene and polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys

In this work, high melt flow rate (MFR) polypropylene (HF‐PP) and polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys (HF‐PP/EPR) with MFR ≈ 30 g/10 min were synthesized by spherical MgCl₂‐supported Ziegler–Natta catalyst with cyclohexylmethyldimethoxysilane (CHMDMS) or dicyclopentyldimethoxysilane (DCPDMS) as external donor (De). The effects of De on polymerization activity, chain structure, mechanical properties, and phase morphology of HF‐PP and HF‐PP/EPR were studied. Adding CHMDMS caused more sensitive change of the polymers MFR with H₂ than DCPDMS, and produced PP/EPR alloys containing more random ethylene‐propylene copolymer (r‐EP) and segmented ethylene‐propylene copolymer (s‐EP). CHMDMS also caused formation of s‐EP with higher level of blockiness than DCPDMS. HF‐PP/EPR alloy prepared in the presence of DCPDMS exhibited higher flexural properties but lower impact strength than that prepared with CHMDMS. Toughening efficiency of the rubber phase was nearly the same in the alloys prepared using CHMDMS or DCPDMS as De, but stiffness of the alloy can be improved by using DCPDMS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42984.     

Structure and properties of polypropylene alloy in situ blends

A series of polypropylene (PP) alloys containing different ethylene contents have been prepared by the in situ sequential polymerization technique, using Ziegler–Natta catalyst (MgCl₂/TiCl₄/BMF; BMF is 9,9‐bis(methoxymethyl)fluorine, as an internal donor) without any external donor. The structure and properties of PP alloys obtained have been investigated by nuclear magnetic resonance, Fourier transform infrared spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, and scanning electron microscopy (SEM). The results have suggested that PP alloys are the complex mixtures containing PP, the copolymer with long sequence ethylene chain, ethylene‐propylene rubber (EPR), and block copolymer etc. In the alloys, PP, EPR, and the copolymer with long sequence ethylene chain are partially compatible. The investigation of the mechanical properties indicates that notched Izod impact strength of PP alloy greatly increases at 16°C/?20°C in comparison with that of pure PP. The noticeable plastic deformation is observed in SEM photograph. The increase in the toughness, the mechanical strength of PP alloy decreases to a certain extent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4804–4810, 2006