成核剂对聚丙烯结晶形态及力学性能的影响

研究了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．采用差示扫描量热法和偏光显微镜分析比较了3种成核剂。结果表明：添加质量分数为0.2％的成核剂,可使PP的结晶峰温度提高15．6～17．8℃。结晶度增加2．5％～10．5％,同时提高了结晶速率,球晶尺寸大幅度降低;试样的拉伸强度、弯曲模量均有提高。弯曲模量提高15．5％～44．9％。     

Rheologically determined negative influence of increasing nucleating agent content on the crystallization of isotactic polypropylene

Dibenzylidene sorbitol (DBS) exists in the form of fibril and usually acts as an effective nucleating agent to facilitate crystallization of polyolefin during manufacturing. In this research, the isothermal crystallization of isotactic polypropylene (iPP) containing different amounts of DBS was followed by dynamic rheometry, and described upon a viewpoint of viscoelastic property evolution. Since the adopted temperatures within the entire sample preparation and characterization process were below the melting point of DBS, the DBS additives played a role of only solid nucleating agent, thus the possible effect of a changed miscibility between iPP and DBS on the viscoelastic properties as change of temperature could be ignored. Although saturation of nucleating iPP was observed at 0.1% DBS concentration, a negative influence with further increasing DBS content on the crystallization of iPP was determined for the first time via time sweep of G′ upon a single angular frequency and application of “inverse quenching” protocol within a wide range of angular frequency. Even more, a largely increased G′ and viscosity were observed in the melt as decreasing the temperature of iPP containing 0.1% DBS, suggesting a strong quasi-solid like behavior before iPP crystallization. A complement for well understanding the crystallization of iPP containing nucleating agent was discussed based on the formation of the DBS fibrils' network, the interfacial tension between crystalline/amorphous phase, and the consistency of crystallizing lamellae. Our study demonstrates clearly that the crystalline characteristic upon saturation of heterogeneous nucleating is difficult to be detected by traditional means, but could be followed reasonably by rheological measurements which is much sensitive to the microstructural changes.     

Influence of a particulate nucleating agent on the quiescent and flow-induced crystallization of isotactic polypropylene

Flow induced crystallization of commercial isotactic polypropylene (iPP) and its blends with sodium 2,2′-methylene bis-(4,6-di-tert-butylphenyl) phosphate (also known as NA11) is studied by means of in-situ time resolved small-angle X-ray scattering (SAXS). The isothermal crystallization at 145 °C (i.e. well below melting temperature of polymer) is performed after the application of steady shear to probe the anisotropic structure formation. In order to separate the influence of shear rate and shear time on polymer crystallization, four different shear conditions (60 s⁻¹ for 1 s, 30 s⁻¹ for 2 s, 15 s⁻¹ for 4 s and 6 s⁻¹ for 10 s) are applied while maintaining the same imposed strain in the polymer melt. Further the effect of different concentration of nucleating agent on the crystallization kinetics of iPP is examined both under quiescent and shear flow conditions. For instance, under quiescent condition, the crystallization half-time (τ_1/2) decreases with the increasing concentration of nucleating agent in the polymer. Under shear flow conditions, our observations are as follows: In the case of neat iPP, τ_1/2 decreases significantly at higher shear rates (≥30 s⁻¹). Compared to the neat iPP, for the same concentration of NA11 in the NA11/iPP blends differences in τ_1/2 with the increase in applied shear rates are significantly smaller. In other words, the crystallization kinetics is dominated by the amount of nucleating agent in the NA11/iPP blends as opposed to shear rates in the neat iPP. The present study shows that the critical value of shear rate required for chain orientation in the molten polymer is lower in the presence of the nucleating agent compared to neat iPP. The self-nucleation process investigated with the aid of differential scanning calorimetry (DSC), indicates that the nucleating efficiency of NA11 on iPP is around 60%.     

Effect of different nucleating agent ratios on the crystallization and properties of MAS glass ceramics

The effects of different kinds of nucleating agents on crystallization, microstructure and performances of Magnesium Aluminosilicate (MgO-Al₂O₃-SiO₂, MAS) glass-ceramics which were fabricated by melting method in this study. Also, this paper systematically investigated the mechanism of glass stability, crystallization kinetics and element distribution of MAS glass-ceramics. Herein, we used three kinds of nucleating agents, which was TiO₂, ZrO₂ and composite nucleating agent (TiO₂/ZrO₂). The results showed after the doping of nucleating agent, the content of α-cordierite was increased, the stability and crystallization kinetics of glass was changed, the precipitated crystal phase was finer and more compact. Wherein, the sample with composite nucleating agents (TiO₂, ZrO₂) has the best performance due to the highest contents of α - cordierite, uniform distribution of elements without agglomeration in the crystal phase and the most compact structure, whose Vickers hardness and bending strength can reach 9.70 GPa and 312 MPa, respectively.     

Comparison of anhydrous and monohydrated forms of orotic acid as crystal nucleating agents for poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

A small molecule nucleating agent, orotic acid (OA), was investigated to enhance crystallinity and crystallization kinetics in poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) for the purpose of addressing embrittlement and reducing solidification time after thermal processing. In particular, the effectiveness of monohydrated (OA-m) and anhydrous (OA-a) forms of OA as nucleating agents for isothermal and non-isothermal crystallization of PHBV films was investigated and compared. Both forms of OA were able to increase crystallization temperature of PHBV as well as form more uniform crystal structures, based on differential scanning calorimetry. It was found that OA-a at 1–2 wt% was most effective in PHBV crystal nucleation because of the increase in overall polymer crystallinity and faster crystallization rate. Additionally, the faster crystallization of OA-a led to fibrillar film morphology of the PHBV/OA blends.     

Quantification of highly oriented nucleating agent in PP-R by IR-microscopy,polarised light microscopy,differential scanning calorimetry and nuclear magnetic resonance spectroscopy

To relate a morphological structure of polymeric specimens to the applied conditions of the production process requires to be able to analyse the morphology and composition of the specimen with high spatial resolution, ideally with a single technique. Infrared microscopy (μFTIR) is a highly attractive technique to map the crystallinity and additive content of polymer samples due to its simplicity and spatial resolution. However, no methods exist yet which allow to exploit these advantages for oriented minority phases with high aspect ratio, and to study the degree of crystallinity in oriented polymer samples. Based on a theoretically derived approach we show for the first time that the spatial distribution of the β-nucleating agent N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide (NU-100) in random ethylene propylene copolymer (PP-R) can be determined by μFTIR from the sum of the absorption intensities in three directions of inspection. Using the same approach the degree of crystallinity of the polymer can be profiled, thus eliminating the problem arising from dichroism inferred by chain orientation. The newly developed method was applied to specimen of PP-R prepared by extrusion, injection and compression moulding. The results regarding the NU-100 content are in good agreement with results from nuclear magnetic resonance (NMR) and the results regarding morphology confirm those from polarised light microscopy (PLM) and differential scanning calorimetry (DSC). This method development opens the perspective to establish process → structure relationships for samples having an arbitrary degree of orientation with regard to the main phase as well as the minority phase.     

浅析成核剂在聚丙烯中的作用

添加成核剂是一种有效的聚丙烯改性方法。聚丙烯成核剂可使聚丙烯结晶度增加、结晶细微化,提高其机械性能等。本文通过介绍聚丙烯成核剂的种类,特性,浅析了成核剂在聚丙烯中作用及其发展。     

成核剂对LLDPE晶体形态及结晶行为的影响

借助原子力显微镜、偏光显微镜和差示扫描量热仪,研究了山梨糖醇类成核剂对线型低密度聚乙烯(LLDPE)晶体形态及结晶行为的影响。结果表明:随着成核剂用量的增加,LLDPE的晶体形态呈均一化,球晶尺寸逐渐减小;成核剂的加入导致了LLDPE结晶温度和结晶度的提高。     

The crystallization behavior and mechanical properties of polylactic acid in the presence of a crystal nucleating agent

The crystallization behavior of polylactic acid (PLA) was studied in the presence of a crystal nucleating agent, ethylenebishydroxystearamide (EBH). The crystallization rate and crystallinity were significantly increased with addition of EBH. The isothermal crystallization half-time at 105°C was decreased from 18.8 minutes for neat PLA to 2.8 minutes for PLA with 1.0 wt % of EBH. The crystallinity of PLA with 1.0 wt % EBH was about 35% after 5-minute annealing at 105°C. Like neat PLA, the double melting peaks were also observed for nucleated PLA. The changes of the double melt peaks were investigated with various crystallization temperatures, heating rates, and annealing times. The heat deflection temperature (HDT) of nucleated PLA was up to 93°C after annealing. The correlation between crystallinity and HDT was demonstrated. A percolation threshold of crystallinity was found corresponding to HDT. The crystal size of nucleated PLA was significantly decreased with addition of EBH. The mechanical properties of annealed PLA blends simultaneously; showed improved modulus and impact strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure and mechanical properties of polylactide copolymer microspheres and capsules

Polylactide homopolymers, polylactide and poly(ethylene oxide) diblock and triblock copolymers are used to prepare spherical microparticles by using the single oil-in-water emulsion and solvent evaporation technique. We are able to create both bulk and hollow microspheres by altering the conditions of preparation. The experiments are carried out at two fixed temperatures of 15 and 22 °C. We show, from scanning electron microscopy data, that the microspheres produced from the homopolymers are bulk and homogeneous at both temperatures whereas they are hollow when the triblock copolymers are used. The diblock copolymers yield bulk microspheres at 15 °C and microcapsules at 22 °C. Compression experiments emphasize once more the inner morphology of the spheres. As it is expected, bulk microspheres have higher Young’s modulus than the microcapsules. Nevertheless, comparative compression analysis of both morphologies shows that the microcapsules retain relatively high compressive moduli. These results have implications for the design of rigid and biodegradable microcapsules.     

Hollow polylactide microcapsules with controlled morphology and thermal and mechanical properties

Hollow polylactide microcapsules were prepared by multistage premix membrane emulsification of polylactide/dichloromethane/oil solutions in water (nonsolvent). The effects of the different oils on the morphology, thermal, and mechanical properties of the hollow microcapsules were investigated. All oils resulted in hollow microcapsules with controlled shell thickness of ～60 nm except for eugenol, in which irregular, massive capsules were obtained. The properties of the microcapsules were strongly dependent on the oil used, for example the thermal transition temperatures found for hollow capsules were lower than for solid particles prepared without any oil. The crystallinity and transition temperatures of the capsules prepared with linear alkanes were higher than for cyclic alkanes; terpenes gave the lowest transition temperatures. The shell stiffness, measured with atomic force microscopy, was highly dependent on the oil used. Capsules prepared with dodecane showed higher stiffness (3.3 N m^?1) than with limonene (2 N m^?1) or cyclohexane (1.4 N m^?1). © 2009 American Institute of Chemical Engineers AIChE J, 2009     

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。     

成核剂对聚丙烯力学性能与结晶行为的影响

研究了两种类型的成核剂对国产共聚聚丙烯的结晶形态以及拉伸强度、冲击强度的影响。结果表明:加入TMB-5型成核剂,聚丙烯的冲击强度有一定程度改善,w(TMB-5)为0.1%时,改性聚丙烯的缺口冲击强度达到最大;TMX-2型成核剂可改善聚丙烯的拉伸性能,但抗冲击性能降低较大;TMB-5型成核剂可显著地改变聚丙烯的结晶行为,诱导聚丙烯在结晶过程中主要形成β晶;TMX-2型成核剂可诱导聚丙烯在结晶过程中主要生成α晶,与纯PP相比,α晶的形成能力增强。     

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。     

Modification of polylactide upon physical properties by solution-cast blends from polylactide and polylactide-grafted dextran

Polylactide (PLA)-grafted polysaccharides with various lengths and numbers of graft chains were synthesized using a trimethylsilyl protection method. The properties of the cast films prepared from graft-copolymers were investigated through thermal and dynamic mechanical analyses. The graft-copolymer films exhibited a lower glass transition temperature (T_g), melting temperature, and crystallinity, and higher viscosity properties compared to PLA films. Moreover, the usefulness of graft-copolymer as a plasticizer was investigated with 1:4 blend films prepared from the graft-copolymers and PLA. The blend films showed lower T_g and crystallinity, and higher viscosity properties compared to PLA films.     

有机磷酸盐类成核剂改性聚丙烯

具有蝶形结构的有机磷酸盐类成核剂HBP能显著改善PP的结晶行为和综合性能。当添加成核剂HBP的质量分数为0．2％时,PP的结晶度从46．4％提高到52．2％,弯曲强度和弯曲模量分别提高了23％和21％,热变形温度和结晶温度分别提高23．9℃和22．7℃,而制品的雾度则降低60％。     

复配对有机硅整理剂成膜形态与应用性能的影响

采用原子力显微镜(AFM)和接触角滴定技术,研究了N-β-氨乙基-γ-氨丙基聚二甲基硅氧烷(ASO)和侧链聚醚/环氧基聚硅氧烷(CGF)溶剂共混组装膜(ASO/CGF)和乳液共混组装膜(AS/CGF)的微观表面形貌、亲疏水性能和其在纯棉织物上的应用性能。结果表明,ASO/CGF膜和AS/CGF膜均存在明显的相分离,其膜的分散相由CGF中聚醚链段吸水团聚堆积而成,连续相为聚二甲基硅氧烷链段(PDMS)。因受到乳胶粒子的限制,AS/CGF膜的相分离特征较ASO/CGF膜明显减小,膜的粗糙度也随之减小,亲水性增加。整理剂的组装膜性能数据可在一定程度反映整理剂的应用性能,对实际应用具有指导和借鉴意义。     

Influence of a nucleating agent on the crystallization behaviour of isotactic polypropylene and elastomer blends

The influence of a nucleating agent on the crystallization behaviour of isotactic polypropylene (iPP), in their blends with poly(styrene-b-ethylene butylene-b-styrene) (SEBS), and a metallocenic ethylene-octene copolymer (EO) was investigated by DSC, optical microscopy and real-time small and wide angle X-ray scattering (SAXS and WAXS) experiments using synchrotron radiation. In non-nucleated iPP/SEBS blends, the crystallization of the iPP matrix occurred in the presence of the styrenic domains which induced a nucleating effect on the process, as observed in the synchrotron experiments. The metallocenic elastomer did not affect the crystallization behaviour of iPP in the iPP/EO blends in non-isothermal experiments, however, the development of crystallinity in the elastomer was restricted. In the nucleated isotactic polypropylene/elastomer blends a significant increase in the crystallinity and the crystallization rate of the iPP matrix was observed due to the presence of the nucleating agent. However, the nucleating efficiency of the additive was strongly affected by the nature and content of the elastomeric component. The nucleating agent efficiency was higher in the presence of the ethylene-octene component than the styrenic elastomer.     

不同单体对成核剂合成的影响

本文介绍了聚烯烃成核剂合成反应所用助剂选择，反应条件的确立，利用均匀设计实现最佳配比实验，进行了不同侧基苯甲醛缩合反应研究。     

Combined effect of nucleating agent and plasticizer on the crystallization behaviour of polylactide

Different plasticized and nucleated polylactide (PLA) systems were prepared and characterized. Two PLA with different l-lactic acid contents (96 and 99.5%) were plasticized with dioctyl adipate (DOA) and nucleated by talc, ethylene bis(stearamide) (EBS), or d-lactic acid-based PLA (PDLA). Crystallization behaviour was studied by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). The combination of plasticizer and nucleating agent was proved to be a very effective approach to improve crystallization velocity of different PLA matrices. Within the studied crystallization temperature range, faster crystallization rates were achieved at lower temperatures. WAXS results indicated the coexistence of α and α′ crystals in all studied systems, except those which showed very low crystallization degrees. Avrami exponent remained constant at around n ≈ 3 for all systems, suggesting equivalent three-dimensional spherulitic growth behaviour regardless crystallization temperature, nucleating agent, and the stereochemistry of the matrix used. Usually, injection-moulding process, where molten polymer is under high pressure, is used for PLA polymer processing. To analyze the effect of pressure on the crystallization process, pressure volume temperature (PVT) measurements were carried out on the systems that showed the fastest crystallization process under atmospheric pressure by DSC. Results showed that the crystallization process was considerably accelerated under pressure.