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1.
成核剂对聚丙烯熔融行为的影响   总被引:2,自引:1,他引:1  
陈彦  徐懋 《高分子学报》1998,23(2):240-243
成核剂对聚丙烯熔融行为的影响陈彦徐懋(中国科学院化学研究所高分子物理开放实验室北京100080)关键词成核剂,聚丙烯,平衡熔点聚合物的熔融过程受分子量大小、分子量分布、分子链构型(等规度、分子结构单元的键接序列)、不同的结晶晶型、不同的热历史等...  相似文献   

2.
等规聚丙烯(PP)是一种具有同质异晶结构的半结晶高分子,呈现α,β,γ,δ和拟六方体5种形态,其结晶结构直接影响PP材料最终的物理与机械性能.研究发现,β晶PP具有良好的冲击韧性和热变形温度高等特点,使用β晶成核剂在PP中诱发稳定的卢晶是目前制备卢晶PP的有效途径.目前报道的PP的β晶成核剂基本上都是小分子化合物,而有关聚合物类β晶成核剂的研究报道很少,2007年Yu等报道了以刚性聚合物(聚苯乙烯等)作为β晶成核剂诱导PP结晶行为的研究.高分子成核剂不仅具有与PP类似的结构,同时在分散性和相容性等方面性能突出.  相似文献   

3.
热致型液晶聚合物的等温和非等温晶化动力学   总被引:2,自引:2,他引:0  
朱珍 《高分子学报》1995,(3):284-290
利用等温和非等温方法详细研究了芳香族聚酯──热致型聚合物对,对’-联苯二甲酸二辛酯的结晶相和液晶相形成机理,并计算了相变过程中的表面自由能与温度系数,研究结果表明:从介晶相开始的结晶过程是二维异相成核、三维线性增长的,而从各向同性液相开始的液晶相形成过程则是二维异相成核二维线性增长的.对两个晶化过程的表面自由能的研究表明,该聚合物液晶相形成过程的相转变表面自由能比结晶过程小得多,预示了它将具有更大的晶化速率.研究还发现,该聚合物的液晶相形成过程具有比结晶过程大得多的温度敏感性.  相似文献   

4.
成核剂和促进剂对聚对苯二甲酸乙二酯结晶的影响   总被引:16,自引:0,他引:16  
研究了一种成核剂和结晶促进剂及其混合物对聚对苯二甲酸乙二酯(PET)结晶过程和熔融行为的影响.结果表明,成核剂的引入降低了PET的结晶成核界面自由能,起到促进PET结晶成核的作用,从而加快了PET的结晶速度.而结晶促进剂对PET的结晶速度影响很小,不能促进PET的成核结晶,但能使PET结晶更完善,使PET的结晶度提高.当两者并用时,PET由熔体降温的结晶行为主要由成核剂控制,而成核促进剂的作用不明显.  相似文献   

5.
成核剂对聚丙烯及其共聚物的结晶行为和性能的影响   总被引:6,自引:0,他引:6  
研究了成核剂1,3:2,4-对二乙基苄叉山梨醇(EDBS)对聚丙烯及其乙烯共聚物的结晶行为和结晶形态的影响,并对其薄膜进行了光学性能的表征。结果表明,添加少量(质量分数0.5%)的成核剂,使聚丙烯样品的结晶温度大大提高,结晶度明显增加。而对于乙烯共聚聚丙烯样品,添加少量(质量分数0.5%)成核剂,不仅使整体结晶温度大大提高,结晶度增加,而且明显强化了低有序部分的结晶。少量成核剂的加入,使聚丙烯及其共聚物的球晶尺寸明显缩小,薄膜的透光性和雾度显著改善。  相似文献   

6.
马来酸酐接枝聚丙烯的等温结晶动力学研究   总被引:17,自引:2,他引:15  
用DSC法追踪了马来酸酐接枝聚丙烯的等温结晶过程,讨论了马来酸酐降低聚丙烯球晶径向生长自由能,提高结晶速率,但降低聚丙烯结晶度的物理和化学机制.同时探讨了马来酸酐的接枝对球晶生长和成核机制的影响.  相似文献   

7.
茂金属间规立构聚丙烯结晶动力学研究   总被引:16,自引:0,他引:16  
用DSC和密度法对茂金属间规立构聚丙烯(sPP)样品进行了等温和非等温结晶动力学研究.测得平衡熔点T0m为158℃,平衡熔融热焓ΔH0m为37kJ/mol,侧表面自由能σ=52erg/cm2,折叠链表面自由能σe=69erg/cm2,链堆砌功q=3375kJ/mol.对非等温结晶过程研究表明,由熔体结晶的sPP具有非均相成核,三维球状生长机理.成核与生长活化能ΔE=731KJ/mol  相似文献   

8.
采用接枝聚合的方法,合成了一种新型聚硅氧烷类向列相液晶共聚物(LCP-H4),然后将LCP-H4与PP在一定工艺条件下密炼共混,得到了一系列的共混样品,采用WAXD、POM与DSC等研究了LCP-H4作为成核剂对PP样品结晶结构、形态与热性能的影响.结果表明,具有独特"液晶"性能的LCP-H4为PP结晶提供了更多的带自由能的晶核与较多的活性点,起到了异相成核的作用,既提高了PP的结晶速度、结晶温度和结晶度,又减小了球晶的尺寸,同时也改变了PP的结晶结构、形态及热力学与动力学,诱导出了β晶.此外,随着增加LCP-H4的含量及结晶温度,对应PP试样的β晶含量(Kβ)呈现先增加后降低的趋势,当LCP-H4含量为0.9%,在128℃等温结晶1h,对应成核PP的Kβ最大,为54%.  相似文献   

9.
孙静  胡建设  钞春英  郭志兴  祁阳 《化学学报》2010,68(10):1003-1009
采用广角X射线衍射(WAXD)与偏光显微镜(POM)等手段研究了硅氧烷液晶共聚物(LCP-O2)作为新型成核剂对聚丙烯(PP)共混样品结晶结构与形态的影响.结果表明,低浓度的LCP-O2在PP共混体系中起到异相成核的作用,使PP的晶核数目增多,球晶细化,并提高了结晶速度,同时也诱导出了β晶的形成.LCP-O2的成核效果主要依赖于其在PP中的相对含量、液晶的分子结构与结晶的热处理过程,且随着结晶温度或成核剂含量的增加,对应PP试样的β晶含量(Kβ)呈现先增加,后降低的趋势.当LCP-O2质量分数为1.0%,在130℃等温结晶1h,对应PP试样的Kβ最大,为58%.此外,属于单斜晶的α球晶呈现黑白颜色,晶束呈放射状生长,边界清晰;而属于三方晶的β球晶亮度要高于α球晶,其颜色艳丽多彩,束状晶片聚集体呈支化生长,内部排列比α晶疏散,边界相对模糊,且β晶与α晶的形态分别在157和171℃完全消失.  相似文献   

10.
通过示差扫描量热仪(DSC)对含氟聚合物与聚醚醚酮(PEEK)共混物的非等温结晶熔融行为和等温结晶熔融行为进行了研究.研究表明:不同的含氟聚合物以及具有不同端基的同种含氟聚合物对PEEK的结晶行为有不同的影响.端基为酰氟(COF)的乙烯-四氟乙烯共聚物(ETFE)能促进PEEK结晶时的成核,加快PEEK的等温结晶速率,而聚四氟乙烯(PTFE)则会减慢PEEK的等温结晶速率.  相似文献   

11.
成核剂对PHBV等温结晶行为的影响   总被引:2,自引:0,他引:2  
用DSC方法测定了氮化硼及滑石粉成核剂对 (β 羟基丁酸酯 与 β 羟基戊酸酯 )共聚物 (简称PHBV)等温结晶行为的影响 .结果表明 ,Avrami方程指数n、成核机理、晶体生长方式基本上不受成核剂的影响 .少量的成核剂可使结晶成核自由能降低 ,结晶速率加大 ,其中氮化硼的效果最为显著  相似文献   

12.
表面接枝改性纳米二氧化硅填充聚丙烯的结晶行为   总被引:13,自引:0,他引:13  
应用差示扫描量热方法研究了纳米二氧化硅 (SiO2 )及其表面接枝改性对聚丙烯 (PP)结晶过程、等温与非等温结晶动力学的影响 ,并研究了上述等温结晶的熔融行为和平衡熔点 .研究发现纳米SiO2 具有明显的异相成核效应 ,能够提高PP的结晶温度、熔融温度、结晶度和结晶速率 ,但降低聚丙烯结晶的完善程度 .粒子的表面接枝处理 ,因改善了粒子与基体的亲和性而有利于粒子成核效应的提高 ,而且此效应尚与粒子的分散相关  相似文献   

13.
The effect of four nucleating agents on the crystallization of isotactic polypropylene (iPP) was studied by differential scanning calorimetry (DSC) under isothermal and non-isothermal conditions. The nucleating agents are: carbon nanofibers (CNF), carbon nanotubes (CNT), lithium benzoate and dimethyl-benzylidene sorbitol. Avrami?s model is used to analyze the isothermal crystallization kinetics of iPP. Based on the increase in crystallization temperature (T c) and the decrease in half-life time (τ½) for crystallization, the most efficient nucleating agents are the CNF and CNT, at concentrations as low as 0.001 mass%. Sorbitol and lithium benzoate show to be less efficient, while the sorbitol needs to be present at concentrations above 0.05 mass% to even act as nucleating agent.  相似文献   

14.
复合成核剂对聚丙烯结晶行为的影响   总被引:8,自引:0,他引:8  
以超细橡胶粒子与有机磷酸盐成核剂复配的方法制备了一种新型复合成核剂,通过示差扫描量热法(DSC)比较了复合成核剂改性PP以及有机磷酸盐成核剂改性PP的结晶温度、等温结晶行为及等温结晶动力学;利用扫描电子显微镜(SEM)的能谱附件和透射电子显微镜(TEM)研究了复合成核剂的微观形态及其在PP中的分散情况.研究结果表明,复合成核剂中超细橡胶粒子作为载体使有机磷酸盐成核剂附着在其表面,提高了成核剂在聚丙烯中的分散性,因而提高了成核剂的成核效率,当成核剂用量较小时,即可明显提高PP的结晶速率和力学性能.  相似文献   

15.
The influences of α/β compound nucleating agents based on octamethylenedicarboxylic dibenzoylhydrazide on crystallization and melting behavior of isotactic polypropylene (iPP) were analyzed. It is found that the crystallization temperatures of nucleated iPP were increased by above 11.0°C and the relative contents of β‐crystals (Kβ ) in iPP reached above 0.40 after addition of compound nucleating agents. The Kβ values depend on cooling rate, crystallization temperature in isothermal crystallization, and the difference between the crystallization temperatures of iPP nucleated by two individual nucleating agents. The nonisothermal crystallization kinetics were studied by Caze method and Mo method, respectively. The effective activation energy was calculated by the Friedman's method. The results illustrate that the half crystallization time was shortened and the crystallization rate was increased obviously after addition of nucleating agents, and the effective activation energy was increased with the relative crystallinity.  相似文献   

16.
The crystallization kinetics of polypropylene and poly (butyl methacrylate-co-hydroxyethyl methacrylate) blend was investigated with differential scanning calorimetry. The isothermal crystallization analysis based on the Avrami theory indicated a heterogeneous nucleating effect from the copolymer. A systematic study of the nonisothermal crystallization kinetics was undertaken using the Avrami equation and its later modifications by Ozawa, Mo, and Zhang. The results demonstrated that the linear relationship failed in the different cooling rates because the Avrami method did not take into account that the crystallization temperature was lowered continuously. The Ozawa and Mo methods could be successful in describing the overall nonisothermal process of polypropylene and the blend. In addition, the nonisothermal crystallization energy values were estimated by the Kissinger and Freidman models. There are two mutually opposite effects on the crystallization behavior of the blend: nucleation ability and growth retardation.  相似文献   

17.
Sodium benzoate (SB), a conventional nucleating agent of α‐phase isotactic polypropylene (iPP) was discovered to induce the creation of β‐phase iPP under certain crystalline conditions. Polarized optical microscopy (POM) and wide angle X‐ray diffraction (WAXD) were carried out to verify the versatile nucleating activity of SB and investigate the influences of SB's content, isothermal crystallization temperature, and crystallization time on the formation of β‐phase iPP. The current experimental results indicated that, under isothermal crystallization conditions, SB showed peculiar nucleating characteristics on inducing iPP crystallization which were different from those of the commercial β form nucleating agent (TMB‐5). The content of β crystal form of iPP nucleated with SB (PP/SB) increased initially with the increase of crystallization temperature, nucleating agent (SB) percentage or crystallization time, reached a maximum value, and then decreased as the crystallization temperature, nucleating agent percentage or crystallization time further increased. While the content of β crystal form of iPP nucleated with TMB‐5 (PP/TMB‐5) showed a completely different changing pattern with the crystallization conditions. The obvious difference of the two kinds of nucleating agents on inducing iPP crystallization can be explained by the versatile nucleating ability of SB. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1183–1192, 2008  相似文献   

18.
The objectives of this paper are to understand the crystallization behavior of polypropylene(PP)composites with surface modified tetra-needle-shaped zinc oxide whisker(T-ZnOw).T-ZnOw was surface modified with different coupling agents,such as silane coupling agents(KH-550,KH-560)and titanate coupling agent(NDZ-105),in order to improve the compatibility between PP and T-ZnOw.DSC and POM were used to characterize the melt and crystallization behavior and the crystalline structures of the composites,respectively.The results show that the surface modified T-ZnOw acts as a nucleating agent of PP crystallization,depending on the coupling agent used for modification.KH-550 and KH-560 have more apparent role in improving the interfacial interaction than NDZ-105 and induce PP crystallization at higher temperature and with smaller spherulites size.The results also suggest that the crystallization behavior depends on not only the content of coupling agent,but also the content of the surface modified T-ZnOw used in the composites.  相似文献   

19.
The effect of nucleating agents on the polymorphic crystallization behavior of poly(butylene adipate) (PBA) was studied with four kinds of commercially available nucleating agents, such as talc and boron nitride. The crystal structures of the α and β forms were studied with wide‐angle X‐ray diffraction. The β‐to‐α‐crystal transformation of PBA in the absence and presence of the nucleating agents in isothermal crystallization and nonisothermal crystallization processes was studied with differential scanning calorimetry and polarized optical microscopy. In both isothermal and nonisothermal crystallization, the introduction of nucleating agents selectively initiated the nucleation of the α‐form crystal, which was relatively slow in the absence of nucleating agents. The nucleating activity of the four kinds of nucleating agents in the crystallization of the PBA α‐form crystal was determined by the study of the nonisothermal crystallization, spherulite morphology, and isothermal kinetics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2340–2351, 2005  相似文献   

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