α成核剂改性聚丙烯等温结晶动力学及晶体形态研究

利用DSC、POM和XRD研究了不同用量α成核剂(二苯亚甲基山梨醇)改性聚丙烯(PP)的等温结晶动力学、晶体形态和结构。结果表明:随着结晶温度的提高,PP和改性PP的结晶速率均降低,α成核剂的加入在高温时可提高PP的结晶速率,但在低温时并不明显;纯PP和添加0.2%α成核剂PP的晶体生长方式或晶体形态随温度升高从片晶向完整球晶结构转变,而α成核剂用量增加会抑制晶体形态的变化,说明体系结晶速率可以控制晶体形态;α成核剂用量为0.4%时,PP的等温结晶速率最快,晶粒最细小,其成核效果最好。     

聚丙烯聚乙烯顺丁橡胶三元共混体系力学性能及光学性能的研究

本文主要讨论了等规聚丙烯/低密度聚乙烯/顺丁橡胶三元共混体系(其中橡胶部分硫化)的力学性能、并用光散射法研究了共混体系的结晶形态及橡胶对等规聚丙烯和低密度聚乙烯共混体系结晶的影响,从光散射强度计算了混合球晶的尺寸。     

成核剂二-(3,4-二甲基苄叉)山梨醇在聚丙烯中的成核效应

研究成核剂二-(3,4-二甲基苄叉)山梨醇(DMDBS)对等规聚丙烯力学性能、光学性能和结晶行为的影响.结果表明:DMDBS可以大幅度提高聚丙烯的力学性能、光学性能和结晶峰温度,具有很好的成核性能.当成核剂DMDBS添加浓度为0.2%时,与空白聚丙烯相比,成核聚丙烯的拉伸强度和弯曲模量可分别提高7.46%和11.96%,雾度可降低52.32%,结晶峰温度T_c可从119℃左右提高到130℃左右.同时,DMDBS的加入可大幅度降低聚丙烯的球晶尺寸.     

聚丙烯/橡胶共混体系——聚丙烯顺丁橡胶改性的研究(Ⅱ)

在等规聚丙烯中掺混高顺式聚丁二烯橡胶,研究了顺丁橡胶改善等规聚丙烯脆性的效果,测定了加入不同比例橡胶的共混物的强度。应用激光小角光散射Hv散射强度分布观察并确定了聚丙烯的结晶变化及形态,计算了球晶尺寸,同时绘出了Vv散射强度图。     

成核剂1,3,5-苯三甲酸三(环己胺)作用下聚丙烯的等温结晶动力学研究

采用经典的Avrami方程研究了成核剂1,3,5-苯三甲酸三(环己胺)(BTCA-TCHA)作用下等规聚丙烯(iPP)的等温结晶动力学,采用阿仑尼乌斯公式计算了聚丙烯的结晶活化能。结果表明,BTCA-TCHA的加入可明显缩短聚丙烯的半结晶时间(t1/2),加快聚丙烯的结晶速度;BTCA-TCHA的加入对聚丙烯的球晶生长方式基本没有影响,空白聚丙烯和成核聚丙烯的球晶生长方式都是扩散控制的异相成核三维球晶生长。此外,成核剂的加入使聚丙烯的结晶活化能ΔE从空白聚丙烯的370 kJ/mol降低到312 kJ/mol,从而加快聚丙烯的总结晶速率。     

山梨糖醇/稀土复合成核剂对等规聚丙烯非等温结晶行为的影响

采用差示扫描量热仪(DSC)研究了山梨糖醇/稀土复合成核剂不同组成对等规聚丙烯非等温结晶动力学及其熔融行为的影响。动力学分析结果表明莫志深方法很好地描述聚丙烯非等温结晶动力学,用Kissinger公式计算所得非等温结晶活化能表明复合成核剂的加入提高了结晶活化能。结晶形态和熔融行为均依赖于复合成核剂的组成和降温冷却速率,较低的降温速率有利于β晶型的生成,随着降温速率的增加,β晶型的相对含量减少。在较多的β成核剂含量和较低的降温速率条件下,可以获得较高含量的β晶型。     

二苯亚甲基山梨糖醇的性质及用途

二苯亚甲基山梨糖醇,英文名为Dibenzal Sorbitol,是七十年代,由日本化学家浜田、内山二人发明的新型有机凝胶剂。由于它具有持殊优越的凝胶化性能,其应用领域日益广泛,涉及到涂料、高分子加工、粘合剂、污水处理、农药、润滑脂等行业。是一种有着广阔发展前途的精细化工产品。二苯亚甲基山梨糖醇,系山梨糖醇和苯甲醛缩合脱水产物。原料国内易得,工艺过程简单,是值得开发的精细化工产品。现仅对其性质与用途,简述如下。一、理化性质二苯亚甲基山梨糖醇主要物性列于表1。表1 二(?)亚甲基山梨糖醇主要物性外观白色粉末假比重 0.22水分% 0.7凝胶率% 100(乙醇)色相(APHA) 180(15%二甲     

等规聚丙烯在静态条件下的结晶行为北大核心

采用热台偏光显微镜研究了等规聚丙烯(i PP)结晶形态随时间的变化。通过控制目标结晶温度,比较了不同结晶温度条件下,成核速率、球晶生长速率随时间的变化以及温度对结晶完成时间的影响,并讨论了相对分子质量对结晶速率的影响。结果表明:等温结晶时,晶核数目和球晶直径都与时间呈良好的线性关系;成核速率与球晶生长速率均随温度的升高而逐渐降低;结晶完成时间实际上是球晶生长速率的反映,随温度的升高而增加;相对分子质量对i PP结晶速率的影响程度具有明显的温度依赖性,温度较低时,影响不明显,随着温度的升高,影响逐渐增大,并且成核时间和结晶完成时间均随着相对分子质量的增加而增加。     

等规聚丙烯在静态条件下的结晶行为

采用热台偏光显微镜研究了等规聚丙烯(i PP)结晶形态随时间的变化。通过控制目标结晶温度,比较了不同结晶温度条件下,成核速率、球晶生长速率随时间的变化以及温度对结晶完成时间的影响,并讨论了相对分子质量对结晶速率的影响。结果表明:等温结晶时,晶核数目和球晶直径都与时间呈良好的线性关系;成核速率与球晶生长速率均随温度的升高而逐渐降低;结晶完成时间实际上是球晶生长速率的反映,随温度的升高而增加;相对分子质量对i PP结晶速率的影响程度具有明显的温度依赖性,温度较低时,影响不明显,随着温度的升高,影响逐渐增大,并且成核时间和结晶完成时间均随着相对分子质量的增加而增加。     

用偏光显微镜研究改性聚丙烯的形态结构——制品直接切片方法

<正> 等规聚丙烯的结晶形态,对制品的力学性能有很大的影响。而晶体形态的生长,又与加工条件有密切的关系[1、2、3、4],用偏光显微镜研究球晶的形态,其中包括聚丙烯及其复合物的结构,可以获得形态结构的资料,这方面的研究工作,早在五十年代已有报导     

Combined effect of shear and nucleating agent on the multilayered structure of injection‐molded bar of isotactic polypropylene

Molten polymers are usually exposed to varying levels of shear flow and temperature gradient in most processing operations. Many studies have revealed that the crystallization and morphology are significantly affected under shear. A so‐called “skin‐core” structure is usually formed in injection‐molded semicrystalline polymers such as isotactic polypropylene (iPP) or polyethylene (PE). In addition, the presence of nucleating agent has great effect on the multilayered structure formed during injection molding. To further understand the morphological development in injection‐molded products with nucleating agent, iPP with and without dibenzylidene sorbitol (DBS) were molded via both dynamic packing injection molding (DPIM) and conventional injection molding. The structure of these injection‐molded bars was investigated layer by layer via SEM, DSC, and 2 days‐WAXD. The results indicated that the addition of DBS had similar effect on the crystal size and its distribution as shear, although the later decreased the crystal size more obviously. The combination of shear and DBS lead to the formation of smaller spherulites with more uniform size distribution in the injection‐molded bars of iPP. A high value of c‐axis orientation degree in the whole range from the skin to the area near the core center was obtained in the samples molded via DPIM with or without DBS, while in samples obtained via conventional injection molding, the orientation degree decreased gradually from the skin to the core and the decreasing trend became more obvious as the concentration of DBS increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

振动注塑对IPP/HDPE共混物力学性能和凝聚态结构的影响

研究了振动频率、振动压力对等规聚丙烯/高密度聚乙烯(IPP/HDPE)共混物力学性能和凝聚态结构的影响。结果表明,与未施加振动的静态试样相比,振动试样的力学性能得到提高。随着振动压力的提高,低频率振动试样的力学性能呈明显上升趋势;振动频率对低振动压力试样的力学性能影响较小。在试样的表层及次表层,聚合物晶体沿熔体流动方向均有明显的取向。而对于试样芯层,则只有在成型温度为190℃、振动频率为0.23 Hz、振动压力为90 MPa的条件下才能观察到明显的晶体取向。     

Effect of 1,3-2,4-di(p-hydroxyl) Benzylidene Sorbitol on Mechanical Properties of Isotactic Polypropylene

The compound 1,3-2,4-di(p-hydroxyl) benzylidene sorbitol, acted as an effective nucleating agent, was synthesized by acetal method from p-hydroxyl benzaldehyde and D-sorbitol. The influence of nucleating agent concentration on crystallization morphology and mechanical properties of isotactic polypropylene (IPP) was investigated using polarization microscope (PLM) and CMT6104 microcomputer control universal test machine. The results showed that crystallinity of IPP increased and spherulite size tended to decline with increasing nucleating agent, because of nucleating agent showed a heterogeneous nucleation effect. IPP with 0.2 wt% nucleating agent show a considerable improvement in mechanical properties.     

Effect of nucleating agent addition on crystallization of isotactic polypropylene

The isothermal and nonisothermal crystallization kinetics of nonnucleated and nucleated isotactic polypropylene (iPP) were investigated by DSC and a polarized light microscope with a hot stage. Dibenzylidene sorbitol (DBS) was used as a nucleating agent. It was found that the crystallization rate increased with the addition of DBS. The influence of DBS on fold surface energy, σ_e, was examined by the Hoffman and Lauritzen nucleation theory. It showed that σ_e decreased with the addition of DBS, suggesting that DBS is an effective nucleating agent for iPP. Ozawa's theory was used to study the nonisothermal crystallization. It was found that the crystallization temperature for the nucleated iPP was higher than that for nonnucleated iPP. The addition of DBS reduced the Ozawa exponent, suggesting a change in spherulite morphology. The cooling crystallization function has a negative exponent on the crystallization temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2089–2095, 1998     

成核剂1，3：2，4-二（亚苄基）-D山梨醇对PET／PEN共混体系结构和结晶形态影响

利用差示扫描量热仪、X射线衍射仪、正交偏光显微镜研究了成核剂1，3:2，4-二(亚苄基)-D山梨醇(DBS)对聚对苯二甲酸乙二醇酯(PET)/聚2，6-萘二甲酸乙二醇酯(PEN)共混体系的结构及结晶形态的影响。结果表明：成核剂的加入，使PET/PEN共混体系熔融起始温度升高10℃左右，结晶峰形变尖锐，说明加入成核剂后有效促进了PET/PEN共混体系的结晶。实验结果表明：成核剂含量低于1％时，PET/PEN共混体系晶体的球晶完整。成核剂含量大于3％时，PET/PEN/DBS共混体系晶体的球晶碎小。成核剂的加入，能够有效地减小球晶尺寸和降低球晶的完善性.     

Effects of solvents and temperature on spherulites of self-assembled phloroglucinol tristearate

Herein, phloroglucinol tristearate (PhgTS) was used to study the crystallization process due to its unique symmetric structure containing a benzene ring and three aliphatic chains. Spherulites of crystallized PhgTS from four solvents under diverse conditions were analyzed in detail and their formation process was studied. Maltese cross is shown by PhgTS spherulites obtained from aprotic solvents via polarized optical microscopy. In comparison, no Maltese cross can be observed from branch-like crystals formed from protic solvents. Independent on the microscaled morphology, lamellae were found to be the basic blocks constructing both PhgTS spherulites and branch-like crystals, which were formed predominantly by stacked PhgTS molecules. Although differential characters of the solvents did not affect the formation of lamellas, the solvents played a crucial role in the formation of self-assembled microscaled morphologies. In particular, the morphologies of spherulites were strongly affected by the concentration of PhgTS solutions, surrounding temperature and evaporation rate of solvents. Generally, a higher concentration of PhgTS led to more homogeneous spherulites, a lower evaporation rate resulted in more compact spherulites, and a higher surrounding temperature generated preferentially more ring-banded spherulites of PhgTS.     

Study on crystalline morphology of poly(l-lactide)-poly(ethylene glycol) diblock copolymer

Crystallization behavior, structural development and morphology evolution in a series of diblock copolymers of poly(l-lactide)-block-poly(ethylene glycol) (PLLA-b-PEG) were investigated via differential scanning calorimetry, wide-angle X-ray diffraction, polarized optical microscopy and atomic force microscopy. In these copolymers, both blocks are crystallizable and biocompatible. It was interesting that these PLLA-b-PEG diblock copolymers could form spherulites with banded textures, which was undercooling dependent. Single crystals with an abundance of screw dislocations were also observed via AFM. Such results indicated that these ringed spherulites and single crystals were formed during the crystallization of the PLLA blocks.     

Charge distribution and crystalline structure in polyethylene nucleated with sorbitol

The charge distribution in samples under direct current electrical field was measured by the pulsed electro-acoustic method, which showed that the space charges were greatly decreased and field distribution tended to be uniform in low-density polyethylene (LDPE) by adding 0.3 wt % bis-(p-ethylbenzylidene)sorbitol. The crystalline structures of LDPE and LDPE/sorbitol were studied. The non-isothermal crystallization kinetics were investigated by differential scanning calorimetry, which showed that sorbitol increases crystallization temperature and crystallinity, but lowers the Avrami exponent of crystallization. The results of wide-angle X-ray diffraction (WAXD) and small-angle light scattering (SALS) experiments show that the crystal form does not change, whereas the perfection of spherulites degrades in the presence of sorbitol. In addition to the obvious difference in crystalline morphology, observed by scanning electron microscopy, the spherulites in the LDPE/sorbitol sample are smaller in size and more in number than those of LDPE. It is well known that in semicrystalline polymers, impurities are expelled from crystalline regions into amorphous regions or interfaces of spherulites. The decrease of space charges can probably be attributed to the uniform distribution of impurities in the whole material, with smaller and imperfect spherulites. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 611–619, 2001     

Crystallization behavior of polypropylene in polypropylene/nylon 6 blend

This article describes the crystallization behavior of polypropylene (PP) in the presence of a crystallizable polymer, namely, nylon 6, in the binary blend of PP/nylon 6 in the composition range from 0 to 30 wt % of nylon 6 content in the blend. The crystallization behavior was studied through variation of the crystallinity with the blend composition and changes in the crystallization exotherms were recorded by differential scanning calorimetry (DSC) and the spherulite morphology was observed via polarized light microscopy (PLM). Comparison of the crystallization exotherms and melting endotherms revealed some differences which are attributed to the role of a sufficiently high thermal energy of the nylon 6 crystals on the melting of PP. The crystallinity of PP decreased in the presence of nylon 6, whereas the crystallinity of nylon 6 increased considerably in the presence of PP. The rate of nucleation of PP on addition of nylon 6 decreased rapidly in the region 0–10 wt % nylon 6 content, and, thereafter, at a higher nylon 6 content, decrease of the nucleation rate was relatively slow. PLM observation revealed the presence of composite spherulites with PP spherulites grown on the surface of the already‐formed nylon 6 spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1153–1161, 1999     

Effect of diluents on the crystallization behavior of poly(4‐methyl‐1‐pentene) and membrane morphology via thermally induced phase separation

The effect of diluents on polymer crystallization and membrane morphology via thermally induced phase separation(TIPS) were studied by changing the composition of the mixed‐diluents systematically, in the system of poly(4‐methyl‐1‐pentene) (TPX)/dibutyl‐phthalate (DBP)/di‐n‐octyl‐phthalate (D‐n‐OP) with TPX concentration of 30 wt %. The TPX crystallization was observed with differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). The membranes were characterized with scanning electron microscopy (SEM), porosity, and pore size measurement. As the content of D‐n‐OP increased in mixed‐diluents, the solubility with TPX increased, inducing the phase separation changing from liquid–liquid phase separation into solid–liquid phase separation, which changed the membrane morphology and structure. When the ratios of DBP to D‐n‐OP were 10 : 0, 7 : 3; 5 : 5, and 3 : 7, membranes were formed with cellular structure and well connected pores, while the ratio was 0 : 10, discernable spherulities were found with not well‐formed pore structure. The effect of composition of the mixed‐diluents on membrane morphology was more remarkable in TPX/dioctyl‐sebacate (DOS)/dimethyl‐phthalate (DMP) system, since good cellular structure was formed when the ratios of DOS to DMP were 10 : 0, 7 : 3, while spherulites were observed when 5 : 5. Dual endotherm peaks behavior on DSC melting curves emerged for all the samples in this study, which was attributed to the special polymer crystallization behavior, primary crystallization, and secondary crystallization occurred when quenching the samples. As the content of D‐n‐OP increased, the secondary crystallization enhanced which induced the first endotherm peak on DSC melting curves moving to a lower temperature and the broadening of the overall melting peak, as well as the increasing of the overall crystallinity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008