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％。     

有机磷酸盐类成核剂的研究进展

介绍了聚丙烯成核剂中有机磷酸盐类成核剂的研究状况,着重介绍了其在PP中的应用研究情况。特别是与其他助剂的协同作用,并提出了我国有机磷酸盐类成核剂的发展建议。     

有机磷酸盐成核剂粒径对PP性能的影响

通过调控反溶剂法中的转速、反溶剂与溶剂配比、溶液浓度等条件制备了不同粒径的2,2’–亚甲基双(4,6–二叔丁基苯基)磷酸钠(NA–40)成核剂,考察了NA–40粒径对等规聚丙烯(i PP)力学性能的影响,并利用差示扫描量热(DSC)仪研究了NA–40粒径对i PP结晶性能的影响。结果表明,随着NA–40粒径的增加,NA–40对i PP力学性能的改善作用变弱。NA–40平均粒径为(17.7±2.2)μm时,i PP/NA–40–1的弯曲弹性模量、弯曲强度和拉伸强度与纯i PP相比,分别提高了44.5%,20.5%和8.3%,相应的缺口冲击强度有所降低;当NA–40平均粒径为(52.6±1.1)μm时,i PP/NA–40–4的弯曲弹性模量、弯曲强度和拉伸强度的增幅分别降至16.8%,2.3%和6.4%。在较低的降温速率下,NA–40粒径对结晶峰值温度(Tc)的影响不明显,提高降温速率对Tc的影响开始显现。用扫描电子显微镜观察NA–40形貌发现,NA–40呈棒状,加工过程影响NA–40粒径,但对NA–40形貌没有影响。利用偏光显微镜观察NA–40在i PP熔体中的分散性,粒径较小的NA–40能够均匀分散在i PP熔体中,而粒径较大的分散性差,大大降低了NA–40的有效成核浓度,影响了NA–40对i PP力学性能及结晶性能的改善作用。     

有机磷酸盐类成核剂对PP性能的影响

研究了4种有机磷酸盐类成核剂对聚丙烯性能的影响。结果表明，这几种有机磷酸盐类成核剂可以有效地改善聚丙烯性能，制得高强度、高耐热透明聚丙烯．合成的有机磷酸盐类成核剂应用效果良好。     

山梨糖醇类及有机磷酸盐类成核剂对聚丙烯性能的影响

利用力学性能测试、偏光显微镜、光电雾度仪及差热分析仪分别考察了山梨糖醇类成核剂(TM-3)和有机磷酸盐类成核剂(NA-21)对聚丙烯(PP)透明性、结晶性能及力学性能的影响。结果表明:NA-21和TM-3对PP均有明显增透的作用;NA-21比TM-3更能提高PP的结晶温度,而TM-3比NA-21更能提高PP的结晶度;TM-3的加入能明显提高PP的冲击强度,而NA-21的加入能明显提高PP的拉伸强度。     

有机羧酸盐类聚丙烯成核剂的研究进展

介绍了有机羧酸盐类成核剂的种类、特点及在聚丙烯中的应用效果,特别是与其他助剂的协同效应,能诱导聚丙烯产生高含量的β晶。综述了该类成核剂在国内外的研究开发进展。     

有机成核剂在聚丙烯改性中的应用

介绍了聚丙烯成核剂对聚丙烯的改性效果以及种类。重点介绍了羧酸金属盐类成核荆、有机磷酸金属盐类成核剂、山梨醇苄叉衍生物类成核剂以及稠环化合物类成核荆等有机成核剂对聚丙烯性能的改善,各类有机成核剂在聚丙烯改性中的成核机理,研究进展以及应用。并对改性聚丙烯有机成核剂的发展方向和前景进行了展望。     

有机磷酸盐类成核剂对PP性能的影响

研究了4种有机磷酸盐类成核剂对聚丙烯性能的影响。结果表明，这几种有机磷酸盐类成核剂可以有效地改善聚丙烯性能，制得高强度、高耐热透明聚丙烯。合成的有机磷酸盐类成核剂应用效果良好。     

不同成核剂成核聚丙烯的结晶行为与力学性能

制备了６种成核剂成核聚丙烯（ＰＰ）母料研究了成核母料和成核母料／ＰＰ的结晶,熔融行为,力学性能和透明性等物理性能,不同成核在成核母材料和成核母料／ＰＰ中对ＰＰ的结晶与熔融行为以及性能有不同的作用,观察到成核型Ａ成核ＰＰ具有较高的结晶温度与综合性能,而成核剂Ｂ成核ＰＰ的透明性较好。     

Heterogeneous nucleating agents for polypropylene crystallization

A model nucleating agent for polypropylene crystallization is described. A series of compounds consisting mainly of organocarboxylic acid salts is evaluated as heterogeneous nucleating agent for polypropylene crystallization by measuring their effect upon the polymer supercooling. Sodium benzoate and basic aluminium dibenzoate were among the best nucleating agents found. The nucleating abilities of the various compounds are discussed in terms of their structural features.     

Acetals as nucleating agents for polypropylene

Nucleating agents increase the impact strength, tensile strength, and tensile elasticity modulus of semicrystalline polymers. Nucleating agents also decrease product cycle times, resulting in a cost savings per product unit. We have synthesized and tested 15 compounds as nucleactors for polypropylene. Of these, trinapthylidene sorbitol, tri-(4-methyl-1-naphthylidene)sorbitol, tri-(4-methoxy-1-naphthylidene) sorbitol, and dibenzylidene xylitol are efficient nucleators of polypropylene. Trinaphthylidene sorbitol (tns) has two major diastereomers: The “S” diastereomer yields a faster crystallization rate for polypropylene than does the commercial nucleator dibenzylidene sorbitol (Millad 3905). Crystallization rates are 208 and 88, respectively (t min^?1 × 1000). The “R” diastereomer, however, is a poor nucleator and interferes with the nucleating activity of the “S” diastereomer. A 52/48 mixture of diastereomers does not nucleate polypropylene, even at twice the concentration. This is first time that the importance of stereochemistry has been demonstrated in the nucleating action. © 1994 John Wiley & Sons, Inc.     

Effects of organic nucleating agents and zinc oxide nanoparticles on isotactic polypropylene crystallization

Organic nucleating agents and inorganic nanoparticles, as well as their hybrid composites, affect the crystallization temperature and morphology of the monoclinic α-form of isotactic polypropylene (iPP). Techniques such as differential scanning calorimetry, hot-stage optical microscopy with cross polars, wide angle X-ray diffraction, and transmission electron microscopy were employed. Nanoparticles of zinc oxide function as efficient supports for 1,3,5-benzene tricarboxylic-(N-2-methylcyclohexyl)triamine because the temperature at which the maximum rate of iPP crystallization occurs during 10 °C/min cooling from the molten state increases from 111 °C for the pure polymer to 125 °C at low concentrations of this hybrid nucleating agent. In the absence of zinc oxide, 0.06 wt% of this aliphatic triamine recrystallizes near 165 °C and increases the crystallization temperature of iPP by 7 °C, relative to the pure polymer. Fluorinated aromatic triamines, such as 1,3,5-benzene tricaboxylic-(N-4-fluorophenyl)triamine, are weak nucleating agents that reduce spherulite size in isotactic polypropylene but only increase the crystallization temperature marginally when the polymer is cooled from the molten state. Both micro- and nanoparticles of zinc oxide reduce spherulite size in isotactic polypropylene, but smaller spherulites are observed when the inorganic nanoparticles exhibit dimensions on the order of 40-150 nm relative to micron-size particles. In contrast, 0.06 wt% of the aliphatic triamine in iPP yields a distorted birefringent texture under cross polars that is not spherulitic. Non-spherulitic birefringent textures in iPP are also observed when the aliphatic triamine nucleating agent is coated onto micro- or nanoparticles of zinc oxide. This study demonstrates that the nonisothermal crystallization temperature of isotactic polypropylene increases by an additional 7 °C when an aliphatic triamine is distributed efficiently within the polymeric matrix by coating this nucleating agent onto zinc oxide nanoparticles.     

Pimelic acid-based nucleating agents for hexagonal crystalline polypropylene

Isotactic polypropylene (PP) resin was doped with pimelic acid, sodium pimelate, and calcium pimelate to stimulate the growth of hexagonal crystalline polypropylene (β-PP). The doped resin was crystallized in a differential scanning calorimeter (DSC) and during compression molding and injection molding. The effect of the additives on the formation of β-PP was examined using DSC and wide angle X-ray scattering (WAXS). Pimelic acid alone was found ineffective while the pimelates induced 64% to 90% of β-growth depending on the nucleating agent system and crystallization condition. In particular, the pimelic acid/calcium stearate system produced a more consistent and higher yield of β-PP. This was attributed to finer particle size and better dispersion of the nucleating agent.     

The effect of nucleating agents on glycerol monostearate antistat performance in three polypropylene resins

The effect of polypropylene nucleation on glycerol ester antistat performance is studied by measuring the electrostatic decay times of injection molded specimens. Behaviors in homopolymer, random copolymer, and block copolymer are compared. Antistat performance is related to crystallinity using DSC.     

Crystallization characteristics of isotactic polypropylene with and without nucleating agents

Nucleation effects of two sorbitol derivatives on the crystallization of isotactic polypropylene (iPP) were studied by means of differential scanning calorimetry (DSC) and polarized optical microscopy (POM). A nonisothermal crystallization kinetic equation was employed to analyze the crystallization characteristics of iPP with or without the nucleating agents from DSC crystallization thermograms. The equilibrium melting temperature of iPP necessary for the kinetic study was obtained by the extrapolation method to be 209°C. The nonisothermal crystallization kinetic analysis for the unnucleated iPP at different cooling rates was possible by assuming the spherulite growth initiated simultaneously by heterogeneous and homogeneous nucleation. On the other hand, the crystallization kinetics of the nucleated iPP could be described by the heterogeneous nucleation and growth process alone. The addition of the nucleating agents up to their saturation concentrations in iPP increased the crystallization peak temperature by 17°C, and the number of effective nuclei by three orders of magnitude. A high concentration of the nucleating agents caused agglomeration of the agents to lower the number of effective nuclei.     

Preparation of micro/nanocellular polypropylene foam with crystal nucleating agents

Open‐cell, porous microcellular foams with nanofibrillated structures were prepared from high tacticity isotactic polypropylene (i‐PP) with a crystal nucleating and gelling agent. The 1,3:2,4 bis‐O‐(4‐methylbenzylidene)‐d ‐sorbitol gelling agent (Gel‐all MD) was used as the crystal nucleating and gelling agent, which enhanced the crystallization and gelation of i‐PP with a three‐dimensional network of highly connected nanofibrils. The core‐back foam injection molding technique was employed to foam the i‐PP with nitrogen (N₂) at a high expansion ratio, where the crystal nucleating agent induced bubble nucleation and bubble growth in the inter‐lamella region and opened the cell walls with a nanoscale‐fibrillated structure. The effects of the nucleating agent on the open cell content (OCC), density and crystallinity were thoroughly investigated. We prepared open‐cell micro/nanocellular foams with an average cell size of microscale voids of < 5 μm. Nanometer‐scale fibrillated structures were formed on the cell wall of the microscale void, the expansion ratio was five‐fold and the open cell content was over 90%. POLYM. ENG. SCI., 54:2075–2085, 2014. © 2013 Society of Plastics Engineers     

Crystallization characteristics of polypropylene and low ethylene content polypropylene copolymer with and without nucleating agents

In this paper, the crystallization characteristics of polypropylene and low ethylene content polypropylene copolymers with and without nucleating agents were studied by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). In order to determine the nonisothermal crystallization rate of these materials, a new estimation method was introduced. Comparing with the crystallization rate coefficient (CRC), which was proposed by Khanna, we found the new approach is more reasonable. From the analysis of results of DSC and PLM, it can be concluded that nucleating agent is more efficient than it is in PP homopolymer. © 1994 John Wiley & Sons, Inc.     

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。