双峰聚丙烯的合成及性能研究

在小型反应器内合成了双峰聚丙烯(BMPP)和含有成核剂的双峰聚丙烯(BMPP／NA)，考察了试样的结晶、熔融行为和力学性能。BMPP的结晶温度较均聚PP提高5℃(降温速率10℃／min)，结晶速率有一定程度增加；而BMPP／NA的结晶温度较均聚PP提高16．5℃，且结晶速率明显加快。BMPP和BMPP／NA的拉伸强度和弯曲弹性模量较均聚PP有了较大提高。     

超细微化有机磷酸盐成核剂对聚丙烯性能的影响*

采用超临界流体技术制备超细微化有机磷酸盐成核剂，研究了超细微化有机磷酸盐成核剂对聚丙烯(PP)结晶行为及力学性能的影响。采用扫描电子显微镜分析成核剂的微观形貌，通过差示扫描量热法和偏光显微镜分析超细微化处理前后有机磷酸盐成核剂对PP结晶度、结晶温度以及晶粒尺寸的影响。结果表明，经超细微化处理，成核剂微观形貌发生变化，粒径变小，分散更均匀。分别添加0.2份超细微化处理前后的成核剂NA-11，NA-13，均可使PP的结晶峰温度提高，最高达到131.7℃，结晶度显著增加，同时结晶速率提高，球晶尺寸大幅下降，成核剂经超细微化处理后，其结晶成核效果更明显。成核剂可明显提高PP的拉伸强度、弯曲性能和透明性。成核剂超细微化处理后，PP的拉伸、弯曲性能和透明性进一步提高，弯曲弹性模量较纯PP提高48.4%，最小雾度为15.3%。     

云母与成核剂复配改性PP

采用云母和成核剂填充改性聚丙烯(PP),研究了复合材料的力学性能、结晶性能及耐热性能。结果表明:云母可有效提高PP的弯曲强度及模量、悬臂梁缺口冲击强度和耐热性能;少量成核剂NA11和表面活性剂硬脂酸钙可使PP/云母复合材料的拉伸强度、弯曲强度、弯曲模量及悬臂梁缺口冲击强度较纯PP分别提高10.4%,32.9%,92.6%,9.2%,热变形温度由纯PP的105℃提高到135℃;云母及NA11对PP具有异相成核作用,复合材料的结晶温度明显提高,晶粒细化、致密。     

玻璃纤维增强高结晶PP的研究

考察了玻璃纤维(GF)增强高结晶聚丙烯(PP)的力学性能,发现高结晶PP/GF的力学性能较普通PP/GF的提高15%～18%;同时考察了不同增容剂对高结晶PP/GF的力学性能的影响,均聚接枝物拉伸强度、弯曲强度较高,共聚接枝物的冲击强度较高;另外发现在PP/GF中加入山梨醇型α成核剂、芳酰胺类β成核剂后,两者对其性能有较大影响,使其力学性能降低40%以上。     

磷酸酯盐成核剂对聚丙烯性能的影响

以均聚聚丙烯(PP)为基体树脂,通过添加磷酸酯盐类成核剂TMP-1等改性方式,研究了该成核剂在不同添加量下对PP弯曲模量、拉伸屈服强度、悬臂梁缺口冲击强度以及热变形温度等性能的影响,通过差示扫描量热仪(DSC)与带可程序升降温控制热台的偏光显微镜(POM)考察了成核剂对PP结晶性能的影响。力学性能测试及偏光显微镜微观观察表明,磷酸酯盐类成核剂TMP-1可以有效提高PP的弯曲模量、拉伸屈服强度、热变形温度以及结晶速度,但是,悬臂梁缺口冲击强度则会明显下降。同时,测试数据表明,当成核剂TMP-1的添加量为0. 05%时,弯曲模量可以达到最大值(2 253. 82 MPa),与未添加成核剂的纯树脂相比,弯曲模量提高了81. 1%。     

1,3,5-苯三甲酸三(环己胺)在PP中的成核效应

研究了1,3,5–苯三甲酸三(环己胺)(BTCA–TCHA)成核剂的添加量对聚丙烯(PP)拉伸性能、弯曲性能、雾度以及结晶峰温度的影响,并与高效的商用二苄叉山梨醇类成核剂Millad 3988进行了比较。结果表明,成核剂BTCA–TCHA在较低的添加量(质量分数为0.20%左右)就具有非常优异的成核效果。当BTCA–TCHA质量分数为0.2%时,PP的拉伸强度和弯曲弹性模量可分别从纯PP的30.85 MPa和1 530 MPa提高到33.85 MPa和1 720 MPa(分别提高9.73%和12.42%),雾度可从空白PP的80.12%降低到37.25%,降低幅度为53.51%,而冷却速率为20℃/min时其结晶峰温度可比纯PP提高12℃左右,其成核效果与Millad 3988类似。此外,BTCA–TCHA在PP中的添加量存在一饱和值(质量分数为0.2%),当添加量超过该值以后,继续添加成核剂对PP性能的改善效果不明显。     

原位添加α晶成核剂对高熔体强度聚丙烯性能的影响

采用过氧化苯甲酰(BPO)为引发剂,通过一步反应挤出法将接枝单体苯乙烯(St)和端乙烯基硅油(VS)接枝到等规聚丙烯(i PP)上制备高熔体强度聚丙烯(HMSPP),同时在制备过程中原位添加α晶成核剂S20或NA11,考察了两种不同的α晶成核剂对HMSPP的制备及其结晶性能、力学性能和发泡性能的影响。熔体流动速率和分子量分布的测试结果表明,S20或NA11的原位添加没有影响i PP接枝反应的进行;差示扫描量热研究表明,成核剂的加入可以有效促进HMSPP的成核结晶,消除了HMSPP结晶过程中的双结晶峰现象,但成核剂的加入对HMSPP的力学性能并无显著影响。S20或NA11的加入可以有效调控发泡样品的泡孔尺寸,使得泡孔直径从38μm增大到50μm以上,发泡倍率也分别从25倍增大到36倍和37倍。     

玻璃纤维增强煤基抗冲共聚聚丙烯的性能

采用双螺杆挤出共混法制备了短玻璃纤维(GF)改性聚丙烯(PP)2240S的共混物,通过力学性能分析测试、扫描电子显微镜表征、熔体流动速率测试和熔融结晶分析等研究了改性体系的力学性能、显微结构、加工流动性和结晶性能等。结果表明,当GF添加量为30%时,复合体系的弯曲强度、弯曲弹性模量、拉伸强度等较纯PP分别提高约112%,269%和108%,但GF与基体粘结力弱导致冲击强度没有提高;为进一步改善界面作用力,以5%马来酸酐接枝聚丙烯作相容剂,相同GF添加量下PP的弯曲强度达86.99 MPa,弯曲弹性模量达5073 MPa,拉伸强度达78.5 MPa,简支梁缺口冲击强度达14.78 kJ/m2,比纯PP的相关指标分别提高约161%,302%,190%和131%,GF与PP界面粘结力增强,PP的力学性能随GF含量的递增而大幅提高。但GF降低了PP的熔体流动速率,并且体系的结晶温度基本未变,结晶度降低,可能与未产生界面横晶有关。     

不同粒径的PP粉的相对分子质量及其分布、结晶性能和力学性能

采用差示扫描量热仪和凝胶渗透色谱仪研究了PP粉粒径大小对其相对分子质量及分布、结晶行为和力学性能的影响。结果表明,粒径大小对PP粉的相对分子质量及分布、结晶温度、结晶速率、成核能力、力学性能等均有明显的影响。随着粒径的减小,PP粉的数均相对分子质量下降,相对分子质量分布变宽,熔体流动速率逐渐增大;结晶温度和结晶起始温度升高,成核能力增加,起始结晶速率增大,晶粒更加细化均匀;但其拉伸强度和缺口冲击强度有不同程度的下降。     

一种高效酰胺类透明成核剂对聚丙烯性能的影响

研究了一种新型酰胺类成核剂,1,3,5-苯三甲酸三(新戊胺),对等规聚丙烯(iPP)性能的影响。首先,对i PP光学和力学性能进行表征。结果表明,该成核剂在较低的浓度下就展现了较高的成核效果,当添加量为0.3‰(质量分数,下同)时,iPP雾度降低了60.2%,弯曲弹性模量和拉伸强度分别提高了19.7%和13.7%,这说明该成核剂是一种高效的iPP透明成核剂。其次,应用偏光显微镜和差示扫描量热仪分别对iPP晶体形貌和结晶行为进行了表征。结果表明,纯iPP在30 min还未完成结晶过程,结晶速率较慢。加入成核剂后,成核i PP在4 min左右就基本完成了结晶过程,结晶速率大大提高,同时球晶尺寸明显减小。另外,成核剂使i PP结晶温度从121.1℃提高至130.0℃,熔融温度从164.1℃提高至165.8℃。这进一步说明了该成核剂的高效。最后,对纯iPP和成核iPP的等温结晶动力学进行研究,结果表明,该成核剂降低了iPP的Avrami指数n,说明其能够促进iPP的异相成核,从而加快结晶速率。     

两种羧酸盐成核剂的制备及其对聚丙烯的成核效果研究

合成了两种具有相似化学结构的聚丙烯（iPP）α晶型成核剂二环［2.2.1］庚⁃5⁃烯⁃2,3⁃二羧酸钠（NA₁）和二环［2.2.1］庚烷⁃2,3⁃二羧酸钠（NA₂）,研究了其在iPP中的成核效果。首先,利用差示扫描量热仪（DSC）和偏光显微镜（PLM）分别考察了两种成核剂对iPP结晶行为的影响。结果表明,当NA₁和NA₂的含量为0.3 %（质量分数,下同）时,iPP的结晶峰值温度分别提升了14.5 ℃和16.0 ℃。同时,两种成核剂都能够明显细化iPP球晶尺寸。其次,利用广角X射线衍射仪（WXAD）对成核iPP进行了表征,两种成核剂都诱导iPP产生了α晶型,说明均为α晶型成核剂。然后,对成核iPP的力学性能进行了表征。结果表明,随着两种成核剂用量的增加,iPP的拉伸强度和弯曲模量呈现先升高后平稳的趋势。当NA₁和NA₂含量为0.05 %时,成核iPP的拉伸强度较纯iPP分别提升了4.6 %和8.6 %,弯曲模量分别提升了8.2 %和21.7 %;冲击强度基本保持不变。     

Mechanical and thermal characteristics and morphology of polyamide 6/isotactic polypropylene blends in the presence of a β‐nucleating agent

The mechanical and thermal characteristics and morphology of polyamide 6 (PA6)/isotactic polypropylene (iPP) blends (10/90 w/w) prepared with different processing procedures and incorporated with an aryl amide nucleating agent, a kind of β‐nucleating agent (β‐NA) for iPP, were investigated. The yield strength and flexural modulus of the blends decreased as β‐NA was introduced into the blends, whereas the impact strength and elongation at break improved. The crystalline structures of the blends closely depended on (1) the processing conditions and (2) competition between the β‐nucleating effect of β‐NA and the α‐nucleating effect of PA6 for iPP. Scanning electron microscopy, differential scanning calorimetry, and X‐ray diffraction were adopted to reveal the microstructures of the blends. At a low β‐NA content (<0.1 wt %), the α‐phase iPP dominated the blends, whereas the relative content of the β‐phase iPP increased remarkably when the β‐NA content was not less than 0.1 wt %. The processing conditions also showed profound influences on the supermolecular structures of iPP; this resulted in different mechanical properties of the blends. As for PA6, the crystallization behavior and crystalline structure did not exhibit obvious changes, but PA6 did play an important role in the epitaxial crystallization of iPP on PA6. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

基于六氢邻苯二甲酸盐的α/β复合成核剂对聚丙烯性能的影响

将α成核剂六氢邻苯二甲酸钙和β成核剂六氢邻苯二甲酸锌复合得到α/β复合成核剂体系,研究了其对等规聚丙烯（iPP）力学性能和结晶性能的影响,并用Avrami理论研究了成核iPP的等温结晶动力学。结果表明,α/β复合成核剂以特定比例复合可以同时提高iPP的刚性和韧性,其中在复合比例为7∶3时,拉伸强度提升了6.7 %,弯曲模量提升了21.8 %,冲击强度提升了108.2 %。进一步研究了复合成核剂在iPP中的浓度效应,随着总添加量的增加,iPP的结晶温度逐渐增加,力学性能趋于稳定,在添加量达到0.4 %（质量分数,下同）时基本不变,此时冲击强度提升了175.3 %,弯曲模量提升了15.0 %,拉伸强度提升了6.5 %。等温结晶动力学的结果表明,复合成核剂体系的加入可以明显缩短iPP的结晶时间并且降低结晶所需的表面能。     

Crystallization behavior and optical and mechanical properties of isotactic polypropylene nucleated with rosin‐based nucleating agents

Background: Rosin‐based nucleating agents, as natural products, do not have any toxicity; hence they could be used in the industrial processing of polypropylene for the manufacture of food containers. As a result they have been the subject of considerable scientific interest in the literature. In this paper, the non‐isothermal crystallization behavior, and optical and mechanical properties of isotactic polypropylene (iPP) nucleated with rosin‐based nucleating agents are reported. Polarized optical microscopy, scanning electron microscopy and wide‐angle X‐ray diffraction were used to investigate the morphology and crystal structure of iPP with different rosin‐based nucleators. The effects of a 1:1:1 co‐crystal on the properties of iPP were also investigated. Results: The addition of rosin‐based nucleating agents led to the following changes in properties: (a) shortened crystallization half time, (b) decreased size of iPP crystals, (c) slightly increased crystallinity and (d) increased transparency, gloss, flexural modulus and tensile strength. The shrinkage of nucleated iPPs was similar to that of the blank iPP. Conclusion: Rosin‐based nucleating agents in iPP were shown to be effective for nucleating crystals, reducing their size and causing preferential growth along the b‐axis, but suppressing detectable spherulites. The 1:1:1 co‐crystal was effective at 0.2 wt%, a greater concentration giving little additional improvement. Copyright © 2007 Society of Chemical Industry     

Isothermal crystallization behavior and properties of polypropylene/EPR blends nucleated with sodium benzoate

The effect of sodium benzoate on the isothermal crystallization behavior of isotactic polypropylene (iPP)/ethylene–propylene rubber(EPR) blends was investigated using differential scanning calorimetry. Dynamic mechanical and physical properties of the iPP/EPR blends nucleated with sodium benzoate were also measured. It was found that the crystallization behavior and physical properties such as heat deflection temperature (HDT), flexural modulus, and impact strength were strongly affected by the competition between the nucleating effect of EPR attributed to its partial compatibility with iPP and the simple addition of the amorphous component, as well as the nucleating effect of sodium benzoate. High impact strength was achieved by addition of EPR and sodium benzoate to iPP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 201–211, 2002     

分子筛协同有机磷酸盐改性聚丙烯性能的研究

采用直接混合法制得等规聚丙烯(iPP)/分子筛体系和iPP/有机磷酸盐成核剂(NA11)/分子筛体系,研究不同种类分子筛在不同含量下对iPP结晶温度及力学性能的影响,进而研究不同分子筛在低含量下协同有机磷酸盐对iPP体系成核性能的影响,从动力学角度解释了提升原因。结果表明,单独添加分子筛制得的iPP体系,随着分子筛含量的增加,结晶性能和力学性能得到显著提升,不同分子筛对iPP性能的影响不同,ZSM-5型分子筛在含量为5%(质量分数,下同)以上具有促进iPPβ晶型生成的效果;采用直接混合法制得的不同分子筛复配有机磷酸酯钠盐NA11成核剂可提升iPP的力学性能;特别是当0.1%NA11和0.1%4A型分子筛一起添加到iPP中时,可在保证iPP具有较好刚性的同时兼具有良好的韧性,使iPP的弯曲模量提高35.2%、冲击强度提高14.4%,从而达到促进iPP材料刚韧平衡的效果。     

Nucleation effects of sodium and ammonium salts of 2,2′‐methylene‐bis‐(4,6‐di‐t‐butylphenylene)phosphate in isotactic polypropylene

The nucleation ability of isotactic poly(propylene) (iPP) to ammonium 2,2′‐methylene‐bis‐(4,6‐di‐t‐butylphenylene) phosphate (An) was investigated in the present work comparing with sodium 2,2′‐methylene‐bis‐(4,6‐di‐t‐butylphenylene) phosphate (NA‐11). Scanning electron microscope (SEM) revealed the crystalline morphology of both An and NA‐11 with planar surface characteristics. The observation of the fracture surface of nucleation iPP samples by SEM showed An particles were dispersed uniformly in polymer and had a better compatibility with iPP matrix than NA‐11 particles. Differential scanning calorimeter (DSC) showed that the melting temperature of An was 262°C significantly lower than that measured from NA‐11 group (above 400°C). Crystallization behaviors of iPP/NA‐11 and iPP/An were also investigated by DSC analysis, respectively. The results showed the crystallization peak temperature and the crystallinity of iPP/An were almost near to that of iPP/NA‐11. Furthermore, mechanical and optical properties of iPP were strongly improved in the presences of An and NA‐11. The flexural strength of iPP was elevated 34 and 35% and the haze value was reduced from 40.4 to 15.1 and 14.9% by the addition of 0.15 wt% NA‐11 and An, respectively. These results demonstrate that the nucleating agent of An described here is a good nucleating agent for the crystallization of iPP as well as NA‐11. POLYM. ENG. SCI., 55: 22–28, 2015. © 2014 Society of Plastics Engineers     

Optimizing the balance between impact strength and stiffness in polypropylene/elastomer blends by incorporation of a nucleating agent

Isotactic polypropylene (iPP) blends were prepared with two different thermoplastic elastomers, a triblock copolymer styrene–ethylene butylene–styrene (SEBS) and a metallocenic ethylene‐octene copolymer (EO). The mechanical properties and morphology of blends with 0–50 wt% elastomer were studied to determine the influence of the presence of the elastomer on the improvement of toughness. The addition of a nucleating agent as a third component exerted a significant effect on the overall properties. Dynamic mechanical properties, flexural modulus, and impact strength as well as morphology were studied for nucleated and nonnucleated iPP/SEBS and iPP/EO blends. The improvement of impact properties found in binary blends was accompanied by a decrease in stiffness. However, the addition of the nucleating agent provided a good balance between impact strength and stiffness. From the results, SEBS was determined to be a better impact modifier for iPP than EO. The nucleated iPP/SEBS blends demonstrated improved mechanical properties compared with both the nucleated iPP/EO blends and the nonnucleated blends. POLYM. ENG. SCI., 48:80–87, 2008. © 2007 Society of Plastics Engineers     

Crystalline morphology and mechanical properties of isotactic polypropylene composites filled by wollastonite with β‐nucleating surface

Wollastonite‐filled α‐isotactic polypropylene (iPP) and β‐iPP were prepared through introduction of wollastonite (W) and wollastonite with β‐nucleating surface (W_x) in iPP matrix. The α‐ and β‐nucleating ability of wollastonite, crystalline morphology, and mechanical properties of injected iPP filled by wollastonite with different nucleating surface were compared using differential scanning calorimetry, wide‐angle X‐ray diffraction, polarizing optical microscopy, mechanical testing, and scanning electron microscopy. The results indicated that iPP filled by wollastonite with different nucleating surface has different crystalline morphology, melting behavior, and mechanical properties. The W and W_x filled iPP mainly formed α‐ and β‐phase iPP, respectively. The tensile and flexural modulus of iPP/W and iPP/W_x increased with increasing wollastonite content, and the tensile and flexural modulus of iPP/W_x were lower than that of iPP/W. The tensile property, flexural property, and impact strength of iPP/W_x were higher than that of iPP/W and β‐iPP. The synergistic effect of reinforcing of wollastonite and toughening of β‐phase leads to higher mechanical properties. POLYM. COMPOS., 35:1445–1452, 2014. © 2013 Society of Plastics Engineers