Nonisothermal melt-crystallization kinetics of isotactic polypropylene synthesized with a metallocene catalyst and compounded with different quantities of an α nucleator

The nonisothermal crystallization kinetics of a metallocene-made isotactic polypropylene (m-iPP) and its compounds with 0.1 wt % and 0.3 wt % of a sorbitol derivative [1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS); an α nucleator] were investigated by differential scanning calorimetry at different cooling rates from the melt. The nucleation efficiency was proved by a significant increase in the crystallization temperatures (accompanied by a slight augmentation of the degree of crystallinity and a decrease in the crystal sizes). This increase in the crystallization temperatures led to higher amounts of fractional content in the γ polymorph, even though DMDBS was supposed to be a nucleator for the α form. The Avrami and Ozawa methods effectively described only the early stage of crystallization, whereas a combined Avrami–Ozawa method was valid for the whole crystallization process. The values of the exponent for this method decreased for nucleated samples in the later stage of crystallization, especially in the case of m-iPP with 0.3 wt % DMDBS added (m-iPP03). The activation energy of the process and the surface free energy were also estimated. The production of considerable proportions of the γ polymorph in m-iPP03 corresponded to higher values of the activation energy and lower values of the surface free energy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of substituted aromatic heterocyclic phosphate salts on properties,crystallization, and melting behaviors of isotactic polypropylene

Nucleation effects of 2,2′‐methylene‐bis (4,6‐di‐tert‐butylphenyl) phosphate metal salts as a nucleating agent for isotactic polypropylene (iPP) were investigated with differential scanning calorimeter and polarized optical microscope, and their effects on mechanical, optical, and heat resistance properties of iPP were also studied. The results showed that monovalent metal salts of substituted aromatic heterocyclic phosphate such as sodium salt, lithium salt, and potassium salt had a good performance. With 0.2 wt % of sodium salt, lithium salt, or potassium salt incorporated into iPP, the crystallization peak temperature of iPP could be increased by 13.5, 13.6, and 15.0°C, respectively; the mass fraction of crystallinity of iPP could be increased by about 5%; and crystallization rate was enhanced increasingly. Meanwhile the tensile strength and flexural modulus of iPP could be increased by about 10 and 30%, respectively, and the clarity and heat distortion temperature of iPP could also be improved significantly. But bivalent and trivalent metal salts of substituted aromatic heterocyclic phosphate had little effect on properties of iPP. Meanwhile the morphology study showed that the addition of monovalent sodium salt could decrease the spherulite size of iPP significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4868–4874, 2006     

Modification of the polarity of isotactic polypropylene through blending with oxidized paraffin wax

The modification of the polarity of isotactic polypropylene (iPP) through blending with oxidized paraffin wax (Fischer–Tropsch synthesis) was investigated. The oxidized paraffin wax significantly increased the polar component of the total surface free energy of polypropylene. Modified iPP also showed significantly higher adhesion to the polar substrate, as represented by a crosslinked epoxy‐based resin. The conservation of the good mechanical properties of the blends was observed up to 6 wt % wax. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 529–533, 2004     

Free‐radical grafting of acrylic acid onto isotactic polypropylene using styrene as a comonomer in supercritical carbon dioxide

Free‐radical grafting of acrylic acid (AAc) onto isotactic polypropylene (iPP) using styrene (St) as a comonomer in supercritical carbon dioxide (SCCO₂) medium was studied. The effects of temperature and pressure of reaction on functionalization degree (grafting degree of AAc) of the products were analyzed. The increase of reaction temperature increases the diffusion of monomers and radicals in the disperse reaction system of SCCO₂. In addition, the increase of temperature accelerates the decomposition rate of 2,2′‐azobisisobutyronitrile (AIBN), thus promoting grafting reaction. It was also observed that functionalization degree of the products decreases with the increase of pressure of SCCO₂ in the range of experiment. The effects of comonomer St on the functionalization degree of the products were investigated. The AAc graft degree of the resulting polymer was drastically higher in the present of St. It reached a maximum when the mass ratio of St and AAc was about 0.7 : 1. Because AAc is not sufficiently reactive toward iPP macroradicals, it would be helpful to use a second monomer that can react with them much faster than AAc. St preferentially reacts with the iPP macroradicals to form more stable styrene macroradicals, which then copolymerize with AAc to form branches. The highest functionalization degree was obtained when the AIBN was 0.75 wt %. When the initiator was used excessively, the functionalization degree decreased because of severe chain degradation of the iPP backbone. The morphologies of pure iPP and grafted iPP are different under the polarizing optical microscope. The diameter of the pure iPP spherulites is 20–38 μ and that of the grafted iPP spherulites is reduced with the increase of the functionalization degree of the products. This is proposed to be because the polar grafts formed during the reaction would have a tendency to associate in the hydrophobic PP environment. This might preserve some of the local crystalline order that existed during the reaction in the swollen iPP phase. It can be proven by a DSC cooling investigation that the crystallization temperature increased as the functionalization degree increased. This is proposed to be because the side‐chain of grafting polymer helps to bring about the heterogeneous nucleation in grafting polymer. Therefore, a large number of nuclei can emerge to a lesser supercooling degree. It can be also proven that the percent crystallization decreased as the functionalization degree increased, probably due to the grafted branches, which disrupted the regularity of the chain structure and increased the spacing between the chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2203–2210, 2004     

等通道转角挤出制备自增强等规聚丙烯的结构与性能研究

采用等通道转角挤出方法对等规聚丙烯进行自增强挤出,研究和分析挤出工艺条件与材料结构、性能之间的关系。利用广角X-射线衍射、差示扫描量热分析等手段对材料结构进行表征。结果表明:经过等通道转角挤出后等规聚丙烯的结晶度提高、晶粒细化、熔点提高,形成明显的取向结构,经过3次等通道转角挤出,等规聚丙烯的拉伸强度由挤出前的17.13MPa提高到59.38MPa。     

影响自由基聚合立体定向力的因素

在自由基聚合中,生成间规立构的趋势稍优先于等规立构。通常认为,碳碳双键上取代基的体积效应和极性效应,是加成反应的立体定向力;而作者则认为,极性呈静电排斥效应是决定间规立构含量较优的主要因素。取代基的体积效应具有两个因素同时决定着立体异构的形成,其一是热力学因素,即体积的排斥效应使间规立构含量增加;另一是动力学因素,即在加成反应瞬间影响链末端碳碳单键内旋转的自由度。因此,取代基的存在不仅使得间规立构占主导,而且取代基体积越小,则自由基的碳碳单键内旋转越容易,形成间规立构的比例亦越高;反之则内旋转不自由,形成随机取向(即无规立构)的比例增加。     

基于熔喷过程的等规聚丙烯中拟六方与α混合晶的构成及其稳定性

采用微型熔喷实验机制备得到等规立构聚丙烯熔喷非织造布,采用广角X射线衍射技术研究了熔喷过程中非织造布生产条件对所形成的非织造布中拟六方和α混合晶晶相结构的影响,采用等温热老化方法研究了混合晶的热力学稳定性及拟六方晶向α晶转变的热力学规律。结果表明,受热风牵伸和室温冷却的共同作用,等规立构聚丙烯熔喷非织造布在成型过程中,易形成含α晶型与拟六方晶型的混合晶。混合晶中α晶与拟六方晶型的比例随牵伸风力的增大和熔体冷却成型时温差的减小而增加。温度高于70℃的热老化可促使混合晶中拟六方晶型向α晶型转变。混合晶晶粒尺寸随α型晶体比例增加而增大。     

聚丙烯绝缘材料电导特性与空间电荷研究

为考察聚丙烯作为直流电缆绝缘材料在电气性能上的的可行性,选用等规聚丙烯材料制备测试试样,通过差示扫描量热法测试熔融温度(165℃)和结晶温度(111℃),针对击穿特性、强场电导和空间电荷分布与电荷的消散等电气性能对聚丙烯材料进行测试。击穿强度测试发现:其交流击穿强度明显低于直流击穿强度,交流击穿强度数据的的分散性相对于直流击穿要好。强场电导特性测试发现:在3.3 kV/mm电场下当温度升高到90℃时,材料的强场电导明显升高,达到室温时的2倍。空间电荷实验结果表明聚丙烯在较低的电场强度(10、20 kV/mm)下未出现明显的空间电荷,而在电场强度达到50 kV/mm时,出现了明显的异极性空间电荷。将试样上下电极短接进行短路发现,10、20 kV/mm下加压0.5 h后,经过0.5 h短路放电,试样内部的空间电荷几乎释放完全。而在50 kV/mm下加压0.5 h后,经过1.5 h的短路时间仍然看到试样内部驻留着大量的异极性空间电荷。     

Cooperative effect of molecular orientation and β-form on toughening injection-molded isotactic polypropylene with β-nucleating agent

The toughness of conventional injection-molded isotactic polypropylene bars has been investigated with respect to the notch location and β-nucleating agent. Superior toughness is achieved in the β-nucleated bars with notches near the gate, but is absent in the near-gate bars without β-nucleating agent or in the β-nucleated ones far from the gate. With detailed structural analysis across the sample thickness, it is indicated that in these tough bars, extensive flow close to the surface suppresses the formation of β-form to a large extent but favors the generation of oriented α-form, whereas toward inner region, an opposite tendency is presented with the decay of flow strength and the activation of β-nucleating agent. Allowing that this peculiar hierarchical structure is absent in other two kinds of bars, it is deduced that the cooperative effect of molecular orientation of α-form in the skin layer and rich β-form in the inner region is responsible for the significant toughness enhancement in the β-nucleated bars near the gate. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012