β晶型聚丙烯及其应用

阐述了β与α晶型聚丙烯（PP）性质上的差别、PP分子结构对β成核PP增韧效果的影响以及β晶型PP较α晶型PP韧性提高的微观机理,综述了PP用β成核剂的特点、发展和应用,介绍了β晶型PP在纤维、薄膜、玻璃纤维增强PP以及管道系统等方面的应用。     

α、β成核剂复配对聚丙烯性能的影响

对5种α成核剂以及稀土β成核剂的成核能力进行了评价，考察了单独添加α、β成核剂聚丙烯（PP）性能的差异，详细讨论了α、β成核剂复配对PP微观结构、力学性能及熔融行为的影响。结果表明，添加α、β复配成核剂PP的性能与复配成核剂中α成核剂诱导α晶型的成核能力密切相关，随着α成核剂成核能力的减弱，复配成核PP冲击强度和断裂伸长率提高，弯曲强度、弯曲模量和拉伸强度减小。差示扫描量热（DSC）分析显示，随着α成核剂诱导α晶型成核能力的减弱，β晶熔融峰强度增加。在不提高总结晶度的情况下，添加α成核剂改善PP刚性以及添加β成核剂改善PP韧性的协同效应没有出现。     

β晶型成核剂增韧改性聚丙烯研究

研究了β晶型成核剂及其用量对不同牌号聚丙烯力学性能的影响,并对其进行了正交偏光显微镜观察、DSC和大角X射线衍射分析。研究表明:添加β成核剂后,聚丙烯晶型由α晶型向β晶型转变,韧性大大增强,用量在0.6%时,均聚聚丙烯悬臂梁冲击强度提高了4倍左右,达到最大值,而共聚聚丙烯的增韧效果不是很明显。     

β晶型等规聚丙烯／EPDM体系的结晶和力学性能的研究

研究了β晶型聚丙烯/三元乙丙橡胶(EPDM)的力学性能,通过广角X射线衍射和偏光显微镜对聚丙烯的晶型进行了表征。结果表明:β晶型聚丙烯/EPDM具有较高的冲击强度,与未经β晶成核剂处理的PP/EPDM相比,冲击强度提高1～2倍,聚丙烯β晶增韧和EPDM增韧具有加和效应;β晶型聚丙烯/EPDM的拉伸强度稍低于未经β晶成核剂处理的PP/EPDM;β晶型聚丙烯与α晶相比,球晶尺寸显著降低,晶界模糊,EPDM在其中分散更为均匀。     

汽车保险杠专用料β晶型聚丙烯的研制

向聚丙烯(PP)中加入0．1％的β晶型成核剂，经过双螺杆挤出机造粒，制得β晶型聚丙烯。结果表明：β晶型聚丙烯的悬臂梁缺口冲击强度可达38kJ／m^2，力学性能指标达到汽车保险杠的要求。并通过注射时加入碳酸钙刚性粒子增韧母粒的方法，解决了β晶型PP模塑收缩率大和表面漆膜附着性差的缺点。     

热处理对β成核聚丙烯结晶结构及力学性能的影响

采用广角X衍射(WAXD)研究了热处理对β成核聚丙烯(β—PP)结晶结构的影响，并考察了不同热处理条件下的力学性能。研究表明，随着热处理温度的升高，β—PP的结晶度增大，结晶形态由β晶型逐渐转变为α晶型。当PP完全转化为α晶型时，其拉件强度及弯曲强度提高，而悬臂梁缺口冲击强度和断裂伸长率却降至最低，由韧性材料转变为刚性材料。该结果说明了在生产工艺中控制合适温度的必要性。     

PP结晶过程中α和γ晶型生成的影响因素

采用差示扫描量热法与广角X射线衍射研究了聚丙烯(PP)的结晶形态,考察了结晶温度、外加成核剂、PP熔体流动速率和无规共聚PP中乙烯单体含量等对PP结晶形态的影响。运用PP结晶过程γ晶型与α晶型的共结晶相图,从本质上解释了结晶温度、乙烯单体含量及成核剂对PP结晶形态的影响。结果发现．PP结晶过程可以产生γ晶型,随着结晶温度的升高、成核剂含量和PP中乙烯单体含量的增加、PP熔体流动速率的增大。γ晶型含量增加。质量分数为0．1％的成核剂使PP中γ晶型的质量分数增加了15．6％;成核剂含量进一步增加,γ晶型含量增加变缓;当成核剂质量分数为0．4％时,γ晶型质量分数仅增加了近16．3％。     

α和β成核剂对聚丙烯结晶行为的影响

研究了α和β成核剂对PP结晶行为的影响，采用偏光显微镜、差示扫描量热法（DSC）和广角X衍射（WAXD）对成核PP的结晶形态进行了详细的表征，结果表明，两种成核剂的加入均使结晶向高温方向偏移，结晶速度加快。α成核剂的加入主要是细化了球晶尺寸，结晶规整均匀，从而使结晶度增加；β成核剂的加入诱导了相当部分的α晶向β晶转变，展示了一种完全不同的束状晶片聚集形态，球晶之间没有清晰的界限，从微观上解释了β晶型韧性较α晶型好的成因。     

聚丙烯结晶行为的控制因素

较系统的综述了各种影响聚丙烯(PP)结晶过程、晶型生成及转变的因素,阐明了通过控制PP的结晶行为来制取符合需要的PP制品是一条简便而实效的途径。     

β成核剂/无机粒子/PP复合材料的结晶行为与力学性能研究

用β成核剂WBG对聚丙烯(PP)进行改性,成核剂用量分别为0.1%和0.2%,并在加入0.1%β成核剂WBG的基础上分别添加4%纳米CaCO3和6%蒙脱土,采用X射线衍射和偏光显微镜对PP复合材料的微观结构进行表征,并测试其多种力学性能。结果表明:β成核剂WBG可以使PP所含的主要晶型由α晶型向β晶型转变,与纳米CaCO3并用有协同效应,使PP复合材料的韧性提高,但同时使拉伸强度、弯曲模量等力学性能降低。     

高流动高耐热聚丙烯改性树脂的研究

通过添加α成核剂、过氧化二异丙苯(DCP)改善聚丙烯树脂的高耐热性能和高流动性能,并研究了高流动、高耐热聚丙烯改性树脂的流动性能、耐热性能、拉伸性能和结晶形态。结果表明,随着DCP加入量的增大,聚丙烯树脂的MFR值增加,流动性得到提高;随着α成核剂用量的增加聚丙烯树脂的热变形温度随之提高,当用量为0.3%,聚丙烯树脂的热变形温度由130℃提高到145℃。     

β成核剂对聚丙烯管材性能影响的研究

研究了β晶型成核剂及其用量对聚丙烯管材力学性能的影响,并对其进行了正交偏光显微镜观察以及DSC分析。研究表明:加入β成核剂后,聚丙烯晶型由α转变为β,韧性大大增强,且用量在0.1%时达到最大值。     

成核剂对超微细滑石粉／聚丙烯共混物性能的影响

研究了α和β成核剂对滑石粉／聚丙烯共混物力学性能的影响。结果表明：α成核剂可以提高材料的拉伸强度、弯曲强度、弯曲模量和硬度等,冲击强度略有下降,而β成核剂使其韧性明显增强;α和β成核剂的加入皆使复合体系的耐热性显著提高,与β成核剂相比,β成核剂更能提高共混物的热变形温度。     

Study on Mechanical Properties and Crystallization Behavior of Polypropylene and Its Blends Modified by β Crystalline Form Nucleating Agent

The influence of β crystalline form nucleating agent (β nucleator) on the mechanical properties of homo-polymerized polypropylene (PPH), random-copolymerized polypropylene (PPR), block-copolymerized polypropylene (PPB), and PPH/PPR/PPB blends was studied. Polarized optical microscopy (POM), differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD) were used to characterize the crystalline morphology and behavior. The results indicated that α crystalline form of polypropylene (PP) had transformed to β crystalline form by adding 0.5% β nucleator; in the meantime, the toughness of PP and its blends was enhanced. That is, 0.5% β nucleator helped to improve the notched impact strength of PPH, PPR, and PPH/PPR/PPB blends by 130%, 40%, and 40%, respectively, without losing the tensile strength and flexural strength.     

Mechanical properties,morphology, and crystal structure of polypropylene/chemically modified attapulgite nanocomposites

Atactic polypropylene (aPP) was chemically grafted onto attapulgite (ATP) via the bridge linking of a polymerizable cationic surfactant and poly(octadecyl acrylate) in the presence of ultrasonic oscillation and dicumyl peroxide, and then, the modified ATP was added to a polypropylene (PP) matrix to obtain PP nanocomposites by melt blending. The results of Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy confirmed that aPP and poly(octadecyl acrylate) were chemically grafted onto ATP through a graft polymerization reaction. The results of the mechanical properties testing showed that the addition of modified ATP improved the toughness and strength of PP remarkably. The dynamic mechanical analysis indicated that the modified ATP significantly increased the storage modulus and decreased the glass‐transition temperature of PP. The results of scanning electron microscopy and transmission electron microscopy showed that the modified ATP was uniformly dispersed into the PP matrix as crystal needles; this proved the presence of strong interactions between modified ATP and PP. The crystal structure analysis revealed that the β‐form crystalline of PP was formed within the modified ATP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

α/β复合成核剂调控聚丙烯结晶过程的研究进展

综述了3类广泛应用的α/β复合成核剂对聚丙烯结晶动力学、结晶形态及宏观性能等方面影响的研究进展。总结了影响α/β复合成核剂调控聚丙烯结晶的主要因素在于两种成核剂的成核能力,具体表现为其成核聚丙烯结晶温度(TC)的高低:TC高的成核剂在聚丙烯结晶过程中起主导作用,TC低的成核剂基本不起成核作用,当两者的TC相接近时发生竞争成核。根据这一规律,找出了复合α、β两种成核剂的方法,并列举将其运用到调控聚丙烯的结晶过程中的实例。     

等规聚丙烯与液晶成核剂的共混改性研究

以单丙烯酸酯液晶单体（RLC）为成核剂,通过共混反应法对等规聚丙烯（iPP）进行改性,制备含β晶型的聚丙烯产品（β-iPP）。首先介绍了β-iPP的制备工艺,然后通过偏光显微镜、广角X射线衍射对纯iPP、iPP/RLC共混物的球晶结构进行了分析;最后通过X射线衍射、差示扫描量热分析等测试方法研究共混物的结晶结构、结晶行为和热性能。结果表明,液晶成核剂RLC能够诱导iPP生成β晶型;制备β-iPP的最佳工艺条件是RLC含量为0.5 %（质量分数,下同）,结晶温度为110 ℃;β晶型相比于α晶型处于热力学亚稳态,在升温过程中,会发生β晶向α晶的转变,但较高的升温速率会抑制这一转变。     

Polymorphism in polypropylene fibers

The structure of polypropylene fibers formed by different spinning conditions was studied. The investigations were carried out using wide‐angle X‐ray scattering (WAXS) and small‐angle X‐ray scattering (SAXS) methods. It was stated that in noncolored fibers the mesophase and the monoclinic α forms were formed. The highest content of the mesophase was observed for fibers extruded at the higher temperature and taken at the medium take‐up velocity. In fibers colored with quinacridone pigment the structure containing the monoclinic α and the trigonal β forms was obtained. The highest content of the β form occurred in fibers taken at the lowest take‐up velocity. The increase of the take‐up velocity caused a rapid drop in β form content. In fibers taken at higher velocities only the α form was formed. It was found that the content of different forms as well lamellar thickness depends on crystallization conditions, which were influenced by the formation parameters. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3364–3370, 2003     

Finite strain response, microstructural evolution and β→α phase transformation of crystalline isotactic polypropylene

An experimental study of the finite strain response of annealed α and β crystalline isotactic polypropylene (iPP) was conducted over a range of temperatures (25, 75, 110 and 135 °C) using uniaxial compression tests. Uniaxial compression results indicate nearly identical macroscopic stress vs. strain behavior for α-iPP and for β-iPP to true strains in excess of −1.1 at room temperature despite the different initial morphologies. At larger compressive strains (>1.2), β-iPP shows more rapid strain hardening. The orientation of crystalline planes during straining differs at room temperature from that at high temperature, indicating a change of slip mechanisms as temperature increases. In addition, strain-induced crystallization occurred at the highest temperature examined in α-iPP. A continuous transformation of β crystals to α crystals with inelastic deformation at room temperature was observed and it was facilitated at higher deformation temperatures. Scanning electron microscopy (SEM) observations of deformed β-iPP provide strong evidence that the transformation is achieved via a solid-to-solid mechanism despite the different helical hands in α and β crystal structures. Molecular simulations were used to investigate a conformational defect in the 3₁ helical chains of β-iPP, characterized by a 120° helical jump. The propagation of this conformational defect along molecular chains provides the reversal of helical hand required by the solid-to-solid transformation. The β→α phase transformation in iPP is proposed to be accomplished via a solid transformation that includes slip along β(110) and β(120) planes during shear of the crystal lattice.     

Phase stability and melting behavior of the α and γ phases of nylon 6

The phase stability and melting behavior of nylon 6 were studied by high‐temperature wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). The results show that most of the α phase obtained by a solution‐precipitation process [nylon 6 powder (Sol‐Ny6)] was thermodynamically stable and mainly melted at 221°C; the double melting peaks were related to the melt of α crystals with different degrees of perfection. The γ phase formed by liquid nitrogen quenching (sample LN‐Ny6) melted within the range 193–225°C. The amorphous phase converted into the γ phase below 180°C but into the high‐temperature α phase at 180–200°C. Both were stable over 220°C. α‐ and γ*‐crystalline structures were formed by annealing but were not so stable upon heating. Typical double melting peaks were shown on the DSC curve; melt recrystallization happened within the range 100–200°C. The peak at 210°C was mainly due to the melting of the less perfect crystalline structure of the γ phase and a fraction of the α phase; the one at 219°C was due to the high‐temperature α‐ and γ‐phase crystals. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011