Non-isothermal crystallization kinetics of calcium carbonate-filled β-crystalline phase polypropylene composites

The non-isothermal crystallization behaviour of high purity β-phase and α-phase polypropylene (PP) and their calcium carbonate-filled composites was investigated by means of differential scanning calorimetry. High purity β-PP polymer was prepared by adding an effective β-nucleator consisting of equal amounts of pimelic acid and calcium stearate. The crystallization temperature and crystallization rate coefficient of pure β-PP polymer were considerably higher than those of the α-PP polymer. This was due to the β-PP polymer containing nucleating agents, which act as nuclei for β-spherulites. The calcium carbonate content had little or no effect on the crystallization rate coefficient and Ozawa exponent of the β-phase PP in the composites. On the other hand, the crystallization temperature, crystallization rate coefficient and Ozawa exponent of the α-phase PP composites depended on the calcium carbonate loading. The effect of calcium carbonate additions on the crystallization of α-PP and β-PP is discussed. ©1997 SCI     

Crystallization behavior and melting characteristics of PP nucleated by a novel supported β-nucleating agent

The β-nucleated PP with high β-PP content was prepared by a novel supported β-nucleating agent, which was prepared with pimelic acid supported on nano-CaCO₃ as support. The influences of the content of the support and supported β-nucleating agent, pre-melting temperature (T_melt) and scan rates on crystallization behavior and melting characteristics, and the β-PP content of β-nucleated PP were determined by Differential Scanning Calorimeter (DSC) and Wide-Angle X-ray Diffraction (WAXD). The results indicated that the addition of supported β-nucleating agent markedly increased the crystallization temperature (T_c) of PP. Increasing the content of supported β-nucleating agent slightly increased the T_c, but had no influence on the melting temperatures (T_m) of β-nucleated PP. The T_c and T_m of β-nucleated PP decreased slightly with increasing the content of the support nano-CaCO₃. The effects of scan rates and multiple scans with different T_melt on the crystallization and melting behavior of PP nucleated by supported β-nucleating agent are similar to that of PP nucleated by calcium pimelate (CaHA). The β-PP content above 90 percent was obtained in PP nucleated by supported β-nucleating agent and was not influenced by the content of nano-CaCO₃. The supported β-nucleating agent prepared by supporting pimelic acid on nano-CaCO₃ is a β-nucleating agent with high efficiency and selectivity, and low cost.     

Different β nucleants and the resultant microstructural,fracture, and tensile properties for filled and unfilled ISO polypropylene

This article explores the use of two β nucleants to improve the fracture behavior of filled and unfilled homo‐polypropylene (PP). The first was based upon an organic quinacridone, whereas the second was based upon the inorganic calcium pimelate. Formulations containing various concentrations of nucleant were prepared using single screw extrusion and then characterized by X‐ray diffraction, differential scanning calorimetry (DSC), Izod impact strength, and tensile testing. The quinacridone nucleating agent produced higher levels of β crystallinity and better improvement in strain to failure, whereas the calcium pimelate imparted greater improvement in impact strength regardless of whether the PP was filled or unfilled. No direct relationship between β crystallinity and fracture properties was observed though synergistic enhancement in impact strength was evident. By varying the concentration of calcium carbonate in the calcium pimelate from 10 : 1, 5 : 1, 2 : 1, and 1 : 1 weight composition of calcium carbonate to pimelic acid, similar property enhancements were achieved regardless of composition although the 10 : 1 sample did produce superior elongation to break. The importance of cooling rate on microstructure within each sample was explored via a through the thickness study using DSC and nano‐indenting methods. Variations in the β content through the thickness were related to cooling and found to be independent of sample composition and processing. Elastic properties varied inversely with β content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

不同方法制备的庚二酸钙对改性聚丙烯结晶和熔融行为的影响

分别采用复分解反应法（D-CaPi）、中和反应法（N-CaPi）以及硬脂酸钙与庚二酸共混法（S-CaPi）3种不同方法制备了庚二酸钙,研究了3种庚二酸钙对聚丙烯结晶和熔融行为的影响。利用傅里叶变换红外光谱仪和差示扫描量热仪测试了庚二酸钙的结构及庚二酸钙改性聚丙烯的结晶和熔融行为。结果表明,3种制备方法都可以使庚二酸完全反应得到庚二酸钙;3种庚二酸钙对聚丙烯均有成核能力,其中D-CaPi和N-CaPi使聚丙烯结晶峰温度提高了约4.9 ℃,S-CaPi使聚丙烯结晶峰温度提高了6.5 ℃,同时,S-CaPi对于聚丙烯β晶型得诱导能力明显优于D-CaPi和N-CaPi,可使改性聚丙烯中的β晶型相对含量达到84.5 %。     

Influence of different β‐nucleating agent on crystallization behavior,morphology, and melting characteristic of multiwalled carbon nanotube‐filled isotactic polypropylene nanocomposites

To obtain isotactic polypropylene (iPP) nanocomposites with high β‐crystal content, TMB5, calcium pimelate and calcium pimelate supported on the surface of nano‐CaCO₃ were used as β‐nucleating agent and MWCNT filled β‐nucleated iPP nanocomposites were prepared. The effect of different β‐nucleating agent and MWCNT on the crystallization behavior and morphology, melting characteristic and β‐crystal content of β‐nucleated iPP nanocomposites were investigated by DSC, XRD and POM. The results indicated that addition of MWCNT increased the crystallization temperature of iPP and MWCNT filled iPP nanocomposites mainly formed α‐crystal. The β‐nucleating agent can induce the formation of β‐crystal in MWCNT filled iPP nanocomposites. The β‐nucleating ability and β‐crystal content in MWCNT filled β‐nucleated iPP nanocomposites decreased with increasing MWCNT content and increased with increasing β‐nucleating agent content due to the nucleation competition between MWCNT and β‐nucleating agents. It is found that the calcium pimelate supported on the surface of inorganic particles as β‐nucleating agent has stronger heterogeneous β‐nucleation than calcium pimelate and TMB5. The MWCNT filled iPP nanocomposites with high β‐crystal content can be obtained by supported β‐nucleating agent. POLYM. COMPOS., 36:635–643, 2015. © 2014 Society of Plastics Engineers     

Effect of the composition ratio of pimelic acid/calcium stearate bicomponent nucleator and crystallization temperature on the production of β crystal form in isotactic polypropylene

The influence of the composition ratio of pimelic acid/calcium stearate bicomponent nucleator on the β crystal form content of isotactic polypropylene (iPP) had been studied at the crystallization temperature of 120°C and duration of 30 min. It was found that the β crystal form content increased continuously with increasing amount of calcium stearate at the constant amount of 0.15% pimelic acid. High β crystal form content polypropylene could be produced when the amount of calcium stearate was greater than 0.30% (the mass composition ratio of pimelic acid/calcium stearate was less than 1/2, the mole ratio was less than 1.89/1). It was shown that pimelic acid and calcium stearate could react to produce a high effective β nucleator (calcium pimelate) “in situ” during the melt‐mixing of iPP and the bicomponent nucleator. The influence of crystallization temperatures (100–140°C) on the β crystal form content of iPP had also been studied at the constant composition ratio of 0.15% pimelic acid/0.5% calcium stearate (the calcium pimelate produced in situ was 0.16%, which was calculated from stoichiometry). It was found that the β crystal form content increased continuously with increasing crystallization temperature and it maximized at 130°C. β Crystal form content decreased sharply at the crystallization temperature of 140°C. It was shown that β → α modification transformed between 130 and 140°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

各种羧酸二盐对嵌段共聚聚丙烯的β成核研究

合成了6种己二酸盐、庚二酸盐作为嵌段共聚聚丙烯(PP-B)的成核剂,研究其对PP-B的β成核影响。结果表明,庚二酸钙、庚二酸钡、庚二酸镁均具有明显β成核PP-B的效果,且成核效应由大到小次序为:庚二酸钙、庚二酸钡、庚二酸镁;庚二酸钠是低活性的β成核剂;己二酸盐类中己二酸钠和己二酸钡对PP-B是高效的β-成核剂,二者的成核效果相当。通过差示扫描量热分析(DSC)和力学性能测试表明,当己二酸钠的用量为0.2%(质量分数)时,经β成核改性产物的缺口冲击性能最佳,且KDSC(β晶型相对含量)最大。     

β成核剂含量和退火处理对改性聚丙烯力学性能的影响

采用熔融挤出法制备了β成核剂改性聚丙烯（PP）。研究了成核剂含量和退火处理对β成核剂改性聚丙烯（β-PP）力学性能的影响,采用广角X射线衍射仪、扫描电子显微镜对β-PP的微观结构进行表征和分析。结果表明,β成核剂含量为0.05 %（质量分数,下同）时β-PP力学性能最佳,110 ℃下退火处理1 h能够进一步提高β-PP的改性效果;适宜的成核剂含量和退火处理对诱导PP基体β晶生成及结晶完整有利;退火处理的β-PP冲击断面存在明显塑性变形现象,呈韧性断裂特征。     

Mechanical behavior of CaCO3 particulate-filled β-crystalline phase polypropylene composites

β-crystalline phase polypropylene (PP) composites containing 5, 10, 20, 30, and 40% (by weight) of CaCO₃ filler were prepared by injection molding. The β-form PP was produced by adding a bicomponent β-nucleator consisting of equal amounts of pimelic acid and calcium stearate. The morphology, static tensile, and impact properties of these composites were investigated in this study. Scanning electron microscopy (SEM) observations revealed that the β-spherulites of the polymer matrix of the composites exhibit curved lamellae and sheaf-like structures. The fillers were observed to disperse within the inter-lamellar spacings of the β-PP composite containing 10% calcium carbonate addition. However, the filler particles tend to link together to form larger aggregates when the filler content reaches 20%. Static tensile measurements showed that the elastic modulus of the composites increases with increasing filler content but the yield strength decreases with increasing filler addition. The falling weight Charpy impact test indicated that the β-PP polymer exhibits the highest critical strain energy release rate (G_c) value. However, there was a drastic drop in G_c of the β-PP composites with increasing filler content. The results are discussed and explained in terms of materials morphology.     

A novel highly efficient β‐nucleating agent for polypropylene using nano‐CaCO3 as a support

In order to increase the isotactic content of β‐nucleated polypropylene (β‐iPP) and decrease the cost of its production, the investigation and development of novel highly efficient β‐nucleators are important issues. Nano‐CaCO₃ was used as a support to prepare a supported β‐nucleator, nano‐CaCO₃‐supported calcium pimelate. Fourier transform infrared spectral analysis shows that an in situ chemical reaction takes place between nano‐CaCO₃ and pimelic acid. Differential scanning calorimetry results indicate that the crystallization and melting temperatures of β‐phase in supported β‐nucleator‐nucleated iPP are higher than those of calcium pimelate‐nucleated iPP. The β‐nucleating ability of the supported β‐nucleator is little influenced by the cooling rate and crystallization temperature over a wide range. The decreased content of pimelic acid in the supported β‐nucleator slightly decreases the crystallization temperature of iPP but it has no influence on the content of β‐phase in nucleated iPP. A novel supported β‐nucleator has been successfully synthesized via pimelic acid supported on the surface of CaCO₃. The crystallization temperature of iPP and melting temperature of β‐phase in iPP nucleated using the supported β‐nucleator are higher than those of iPP nucleated using calcium pimelate. The concept of a supported nucleator will provide a new way to increase the efficiency of polymer additives and to decrease the amounts of them that need to be used by using nanoparticles as supports. Copyright © 2010 Society of Chemical Industry     

Effect of carbon nanotube‐supported β nucleating agent on the thermal properties,morphology, and mechanical properties of polyamide 6/isotactic polypropylene blends

A new kind of β nucleating agent, multi‐wall carbon nanotube (MWCNT)‐supported calcium pimelate was introduced into polyamide 6 (PA 6)/isotactic polypropylene (iPP; 10/90 by weight) blend and the thermal properties, morphology, and mechanical properties were investigated. The results showed that β‐iPP appeared at low content of MWCNT‐supported calcium pimelate which surmounted the α‐nucleating effect of PA 6 for iPP, and the content of β‐iPP increased with increasing content of MWCNT‐supported calcium pimelate. The impact strength, elongation at break, and flexural modulus were improved with increasing content of MWCNT‐supported calcium pimelate without significantly deteriorating the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

羧酸金属盐β晶型成核剂合成及应用研究

研究开发了一种新型的羧酸金属盐β晶型成核剂。此成核剂不仅高效诱导β-PP形成，而且成核效率高, β-成核PP的冲击强度可提高2~4倍，并且大幅提高PP热变形温度，有效缓解了聚丙烯制品的冲击强度和热变形温度二者之间的矛盾。目前已在PPR管材和PPH板材、大注件制品以及锂电池隔膜方面得到广泛的应用。     

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。     

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。     

β成核剂对聚丙烯力学性能的影响

通过在抗冲聚丙烯基础树脂中添加自主研制的酰胺型高效β成核剂,在升高聚丙烯耐热温度的同时有效提高聚丙烯树脂EPS30R的冲击强度,研究酰胺型β成核剂PA-01、TMB-5和FB-1添加量对聚丙烯树脂EPS30R力学性能的影响,通过微观形态分析增韧的内在原因,并考察成核剂对聚丙烯树脂EPS30R的成核效果。结果表明,添加β成核剂后,聚丙烯的力学性能明显改善,且β成核剂诱导聚丙烯的成核效果较好。     

己二酸/无水硫酸钙晶须改性PP的等温结晶动力学

通过差示扫描量热(DSC)仪分析了己二酸(AA)和无水硫酸钙晶须(ACSW)复配改性聚丙烯(PP)的等温结晶行为,用偏光显微镜(PLM)观察了AA/ACSW复配改性PP的晶体形貌。DSC分析结果表明,随着结晶温度升高,半结晶时间和最大结晶时间增加,半结晶速率降低;与纯PP相比,ACSW和AA/ACSW复合改性都能使PP的结晶时间降低,结晶效率增加,说明ACSW和AA/ACSW对PP具有异相成核作用,并且AA/ACSW复合改性PP对提高PP的结晶性能有更好的效果,此外ACSW改性PP的等温结晶活化能最低。对改性PP的PLM的观察说明ACSW对PP具有异相成核作用,而AA/ACSW对PP的β晶成核具有协同促进作用。     

Synergistic enhancement of crystallization and mechanical performance of polypropylene random copolymer by strong shear and β‐nucleating agent

Investigation of microstructure and properties is critical for the development and application of polymer materials. Polypropylene random copolymer (PPR) and β‐nucleated PPR are widely used in water pipe production. The effect of melt shear flow on the crystalline structure and mechanical properties of PPR containing β‐nucleating agent needs in‐depth understanding. In this paper, we demonstrated the preparation of PPR and PPR containing 0.1 wt% calcium pimelate (Ca‐Pim) samples by conventional injection molding (CIM) and oscillation shear injection molding (OSIM). The multilayer structures and morphologies of the samples were characterized by SEM, two‐dimensional X‐ray scattering and DSC. The mechanical properties and the microstructures of samples prepared by these two injection molding methods were compared. Compared with samples prepared by CIM, the stronger shear provided by OSIM induced the formation of a thicker layer of a shish‐kebab structure and a higher content of γ crystals, and dramatically suppressed the β‐nucleating effect of Ca‐Pim. The OSIM samples have more shish‐kebab structures and higher crystallinities than CIM samples and therefore the former exhibit better rigidity than the latter. The β crystals in the core layer and the thicker layer of shish‐kebab structure endow OSIM‐PPR/0.1 wt% Ca‐Pim with excellent impact toughness. © 2017 Society of Chemical Industry     

A novel effective way of comprising a β-nucleating agent in isotactic polypropylene (i-PP): Polymerized dispersion and polymer characterization

A kind of β-nucleating agent, namely a stearic acid and stearate lanthanum complex (NAβ), was introduced into isotactic polypropylene (i-PP) via an in situ polymerization method for the first time. A dynamic adhesion model was constructed for interpreting the β-nucleating agent dispersion process. The effects of a polymerized dispersion of the β-nucleating agent on the content of β-crystal and crystallization behavior of i-PP were investigated. The results show that the crystallization peak temperature of thus β-nucleated i-PP was greatly increased while the spherulite size dramatically decreased compared with those of net i-PP. The content of β-phase (k_β value) can reach as high as 88.7% with only 0.135 wt% of NAβ addition, which holds constant with a further increase of NAβ concentration up to 3.41 wt%. The non-isothermal crystallization kinetics of thus β-nucleated i-PP was studied with Mo equation and crystallization activation energy estimated by Kissinger method, giving unique results pertaining to the unprecedented NAβ polymerized dispersion.     

透明聚丙烯的研制

以均聚聚丙烯(PP)为基体树脂，探索了不同牌号的PP、不同类型的成核剂和其它助剂等对透明PP性能的影响，以及加工成型工艺参数对透明PP性能的影响。结果表明，选用T30S型连续均聚PP作透明PP的基体树脂，添加复配后的成核剂，可生产出综合性能优异的透明PP。     

相对分子质量对β晶型等规聚丙烯性能的影响

利用熔体流动速率来反映等规聚丙烯(IPP)的相对分子质量,在添加自制β成核剂的条件下通过力学性能测试、差示扫描量热仪以及X射线衍射仪研究了相对分子质量对β晶型等规聚丙烯(β-PP)热行为、晶型组成和力学性能的影响。结果表明,加入β晶型成核剂后,IPP结晶温度、热变形温度均增加10℃左右,β晶型相对含量增加至60%～70%;相对分子质量较高的β-PP冲击强度提高一倍以上,相对分子质量较低的β-PP冲击性能改善有限;β-PP的弯曲模量和弯曲强度均下降,相对分子质量越低降低幅度越大。