原位交联改性PP/POE共混物的等温结晶行为

采用热塑性聚烯烃弹性体(POE)作为增韧材料,以过氧化二异丙苯(DCP)为交联剂制备了PP/POE共混物。利用差示扫描量热仪(DSC)和偏光显微镜(PLM)研究了PP/POE共混物等温结晶行为,并用Avrami方程分析了PP/POE共混物结晶动力学。结果表明,POE的加入能起到异相成核的作用,加快了PP的结晶成核速率。Avrami指数在1.93～3.09,DCP的引入对聚丙烯(PP)的成核与生长机理影响不大,但其原位交联作用阻碍了PP分子链的运动,使得PP结晶速率降低,结晶时间延长。     

增容作用和动态固化对聚丙烯/环氧树脂共混物形态结构的影响

研究了增容作用和动态固化对聚丙烯(PP)/环氧树脂(EP)共混物形态结构的影响。实验结果表明,PP/EP共混物是不相容共混体系,当环氧树脂含量小于50%时,共混物中环氧树脂以分散相存在,PP为连续相。反之,则共混物的相态发生相反转,即环氧树脂为连续相,PP为分散相。加入马来酸酐接枝聚丙烯(M AH-g-PP)促进环氧树脂与PP的相容性,使得分散相的颗粒明显变小。与PP/EP和PP/M AH-g-PP/EP共混物不同,当环氧树脂含量大于50%时,动态固化PP/EP和PP/M AH-g-PP/EP共混物仍是环氧树脂分散相和PP连续相结构,未出现相反转。对于相同含量环氧树脂的共混物,动态固化PP/M AH-g-PP/EP共混物中环氧树脂分散相尺寸明显小于动态固化PP/EP共混物中环氧树脂分散相尺寸。     

取代芳基杂环磷酸盐类成核剂改性聚丙烯的等温结晶研究

采用差示扫描量热法(DSC)对取代芳基杂环磷酸盐类成核剂改性聚丙烯的等温结晶过程及结晶动力学进行了研究.结果表明取代芳基杂环磷酸的一价金属盐成核剂的加入可大幅度缩短聚丙烯的半结晶时间t1/2,加快聚丙烯的结晶速度,而二价和三价的金属盐对聚丙烯结晶速度的改善不明显.对于iPP及成核iPP,其Avrami指数基本都在3左右,表明在等温条件下成核剂的加入对聚丙烯的结晶方式影响不大.同时采用Hoffman理论计算了聚丙烯和成核聚丙烯球晶生长的单位面积折叠表面自由能σe,结果表明取代芳基杂环磷酸一价金属盐的加入可显著降低聚丙烯的σe,而二价和三价的金属盐对σe的影响不明显.     

液晶聚合物β成核剂/等规聚丙烯的等温结晶动力学和熔融行为

将主链型液晶聚酯(PBDPS)大分子β成核剂与等规聚丙烯(i PP)熔融共混,得到不同添加量的i PP/PBDPS样品。利用差示扫描量热分析、X射线衍射、偏光显微镜等研究了i PP和PBDPS共混物的等温结晶动力学、结晶熔融行为、晶型结构和结晶形态。结果表明,i PP和i PP/PBDPS共混物的等温结晶动力学适用于Avrami方程,Avrami指数(n)从2. 62～2. 81变为2. 60～3. 25,晶体的生长方式为二维生长与三维生长并存。PBDPS起到异相成核作用,i PP结晶速率常数(K)随着PBDPS的添加而增大,半结晶时间(t1/2)随之缩短。使用Arrhenius方程计算了等温结晶活化能,并通过HoffmanWeeks外推法得到了i PP/PBDPS中α、β晶的平衡熔点。液晶高分子PBDPS能有效诱导i PP形成β晶型,β晶含量随着PBDPS添加量与结晶温度的提升而增大,当PBDPS质量分数为4%,结晶温度为130℃时,β晶含量高达92. 5%。     

低等规聚丙烯的等温结晶动力学

利用 DSC法研究了低等规度聚丙烯 ( LIPP)的等温结晶动力学。根据 Avrami方程求出了各个结晶温度下的结晶动力学参数 k( T)、n和 t1/ 2 ,研究了 L IPP的结晶度及结晶速率与结晶温度的关系。利用Hoffman等温结晶理论 ,求出 LIPP的 σe 为 3.0 7× 10 -2 J/ m2 。     

改性纳米SiO2填充PLA/PBAT复合体系的 结晶动力学研究

利用Avrami方程,研究PLA及PLA/PBAT/SiO_2复合材料的等温结晶动力学,研究结果表明:PLA及其共混物的Avrami指数n值分别为2.06~2.29和1.91~3.05;样品的结晶常数K(T)、半结晶时间t_(1/2)和结晶速率τ_(1/2)均随结晶温度的升高先增大后减小;在相同的结晶温度条件下,PLA/PBAT/SiO_2样品的K(T)和t_(1/2)均高于纯PLA的。采用改进的Avrami方程,分析PLA及PLA/PBAT/SiO_2复合材料样品的非等温结晶过程。研究结果表明:PLA及其共混物的Avrami指数n_1数值范围为1.31~4.88,表明晶体生长模式均为二维生长和三维生长并存;所有样品的n_1均随着升温速率的增大而增大,且n_1均小于n2,Z_(c1)和Z_(c2)也随升温速率的增大而增大。基于Mo方程分析结果与基于改进的Avrami方程分析结果一致,进一步证实了纳米SiO_2的引入提高了PLA的结晶速率;且PLA/PBAT/SiO_2样品的结晶活化能ΔE均大于纯PLA的,说明PBAT及SiO_2的引入阻碍了PLA主链的链段向晶体生长表面的迁移过程。     

一种新型释放负离子的聚丙烯塑料的结晶动力学

使用Avrami理论、Hoffmann理论和Ozawa方法对PP和一种新型释放负离子的聚丙烯塑料PPN03的等温结晶动力学和非等温结晶动力学进行了研究。结果表明,PPN03和PP的结晶速率常数、Avrami指数都不相同。说明PPN03单位晶区的侧表面自由能σc要小于PP,而其成核机理和生长方式都会发生变化。     

PP/Talc复合材料的非等温结晶动力学

用差示扫描量热法(DSC)研究聚丙烯(PP)及PP／Talc复合材料的非等温结晶过程,加入滑石粉后,PP／Talc的结晶速率、结晶度得到明显提高。结合Avrami和Ozawa方程得出一个适合于非等温的结晶动力学方程,并由此获得PP／Talc复合材料的非等温结晶动力学参数,计算表明Talc能促进PP材料的结晶。     

结晶动力学评价聚酰胺6/磺化聚苯乙烯(Mn, Na)盐共混物的相容性

用DSC测定的方法在等温条件下研究了聚酰胺6/磺化聚苯乙烯钠盐共混物(PA-6/NaSPS)和聚酰胺6/磺化聚苯乙烯锰盐共混物(PA-6/MnSPS)的结晶动力学。对于PA-6/MnSPS共混物,结晶速率(G)和成核速率(N)既与过冷度(ΔT)有关又与共混物组成(φMnSPS)有关,而PA-6/NaSPS共混物的G和N仅与ΔT有关,与φNaSPS无关。对于PA-6/MnSPS共混物,化学势差(ΔTG=0.005/T0m)和结晶的表面自由能参数(K和S)随φMnSPS的增加而增加,而PA-6/NaSPS共混物的ΔTG=0.005/T0m、K和S几乎不随φNaSPS的变化而变化。这些都说明PA-6/MnSPS共混物是相容的,PA-6/NaSPS是不相容的。     

PP/PP-g-MMA/M复合材料非等温结晶动力学研究

用示差扫描量热法(DSC)考察了聚丙烯(PP)、聚丙烯/云母(PP/M)和聚丙烯/聚(丙烯-g-甲基丙烯酸甲酯)/云母复合材料(PP/PP-g-MMA/M)的非等温结晶过程.用Avrami方程和Ozawa方程对上述过程进行分析,n、t1/2、F(T)、Tp等参数表明,M和PP-g-MMA,特别是PP-g-MMA的掺入改变了PP的结晶成核和生长机理.用Dobreva方法分析填料的成核活性,ε数值表明,M有较强的成核活性,PP-g-MMA的掺入又进一步增强其成核活性,从而使结晶温度明显提高.Kissinger方法的计算结果表明,添加M可使PP的结晶活化能减小,再添加PP-g-MMA又使PP/M复合体系的结晶活化能进一步减小.     

Effects of modified hyperbranched polyester as a curing agent on the morphology and properties of dynamically cured polypropylene/polyurethane blends

The dynamic vulcanization process, usually used for the preparation of thermoplastic elastomers, has been applied to prepare polypropylene (PP)/polyurethane (PU) blends. Boltorn^TM H20 (H20) hyperbranched polyester containing 16 hydroxyl end gropus and pentaerythritol are used as curing agents, respectively, for curing PU oligomer during blending with molten PP. To improve the compatibility of cured PU particles with PP matrix, H20 is partly functionalized with stearic acid. The morphology, mechanical properties, thermal properties and melt flow index (MFI) of the PP/PU blends with different curing agent are investigated. Compared with pentaerythritol, SEM photographs show that H20 partly functionalized with stearic acid effectively reduces the size and size distribution of cured PU particles in PP/PU blends which also is proved by MFI measurement. Consequently, the dynamically cured PP/PU blends with modified H20 have better mechanical properties than those cured with pentaerythritol. The shifts of crystallization peaks to higher temperatures for all PP/PU blends indicate that PU particles in the blends can act as effective nucleating agents. Moreover, due to the smaller size of PU particles PP/PU blends cured with modified H20 have higher crystallization temperatures than those blends cured with pentaerythritol at the same PU content.     

环氧树脂改性双环戊二烯型氰酸酯树脂固化反应性

采用凝胶试验、 FTIR和DSC等手段研究了环氧E-51与双环戊二烯型氰酸酯(DCPDCE)共聚体系的固化反应性以及阶梯固化过程中—OCN基、 三嗪环、 唑啉、 噁唑啉酮的变化情况。结果表明, 环氧树脂既能够催化氰酸酯本身三聚成环反应, 又对氰酸酯三聚成环反应有稀释作用。当环氧树脂含量(环氧占混合物总量的质量百分比)大于5wt％时, 催化效果增加不明显, 稀释作用加强; 当环氧树脂含量约为25wt%时, 以上两种作用效果基本平衡, 改性体系的固化反应活性和纯DCPDCE相当。阶梯固化时, 低温阶段(160~180℃)主要发生生成三嗪环和唑啉的反应, 高温阶段(200~220℃)主要发生三嗪环和唑啉向噁唑啉酮的转化反应。另外, —OCN基的低温转化率随着环氧树脂含量的增大而提高, 固化树脂的最终结构组成和环氧树脂的含量有关。      

聚丙烯/马来酸酐接枝聚丙烯/蒙脱土复合材料的结晶动力学和结晶形态

用示差扫描量热法(DSC)研究了蒙脱土对聚丙烯及马来酸酐接枝聚丙烯的非等温结晶行为的影响;用偏光显微镜(POM)观察了聚丙烯及共混体系的结晶形态,估算了径向生长速率。结果表明,随着蒙脱土加入量的增加,聚丙烯的球晶结构逐渐受到破坏,球晶尺寸变小,径向生长速率降低。     

Effect of elastomer on polypropylene/nylon-12 blends

Various compositions of polypropylene (PP)/nylon-12 blends with elastomer were prepared. Morphologies and mechanical properties of the blends were studied. In particular, the effect of ethylene-propylene (EP) elastomer and maleic anhydride-grafted ethylene propylene elastomer (Ma-g-EP) on the PP/nylon-12 blends were investigated. The results showed that PP/nylon-12 blends have inferior mechanical properties because of their poor compatibility and dispersion. The EP elastomer has a limited effect on the blends since the mechanical properties of PP/nylon-12 blends were controlled by their interface. The Ma-g-EP elastomer improved the mechanical properties of PP/nylon-12 blends through improvement of the interface between PP and nylon-12, and compatibility between the elastomer and nylon-12. Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were used to characterize microstructures. The dispersion of components and the compatibility between PP and nylon-12 were significantly improved with addition of the Ma-g-EP elastomer.     

PP/PC/PP-g-GMA共混物的结晶和相形态

采用偏光和相差显微镜详细研究了聚丙烯(PP)/聚碳酸酯(PC)不相容聚合物共混体系和PP/PC/PP-g-GMA增容共混体系的结晶和相形态.研究结果表明,PP/PC共混体系中增容剂PP-g-GMA中甲基丙烯酸缩水甘油酯(GMA)支链起到成核剂的作用,促进PP结晶异相成核,使得PP有效晶核密度增加,球晶尺寸减小;PC分散...     

嵌段共聚物对PPO／PP共混物的增容作用

研究表明苯乙烯－乙烯／丙烯嵌段共聚物及其混合顺序对聚／聚丙烯共混物形态和性能有一定影响。ＰＰＯ／ＰＰ共混物加入增容剂后，分散相颗粒变得精细均匀，缺口冲击强度大大提高。文中计算了ＳＥＰ／ＰＰＯ及ＳＥＰ／ＰＰ共混物的相互作用能密度Ｂ，计算表明，ＥＰ体积分数高的ＳＥＰ和ＰＰＯ的亲和力比ＳＥＰ与ＰＰ的亲和力小，因此当ＳＥＰ先与ＰＰＯ预混合，然后与ＰＰ混合，ＳＥＰ易于迁移到两相界面，降低了界面张力，减小了分     

Crystal morphology,mechanical property and non-isothermal crystallization kinetics of poly(trimethylene terephthalate)/maleinized poly(ethylene-octene) copolymer binary blends

The crystal morphology, impact strength and nonisothermal crystallization kinetics of poly(trimethylene terephthalate)/maleinized poly(ethylene-octene) (PTT/PEO-MA) copolymer blends were studied by using the polarized optical microscopy, impact tester and differential scanning calorimetry (DSC). Avrami theory modified by Jeziorny, Ozawa and Mo theories were used to study the non-isothermal crystallization kinetics of the blends, respectively. The results suggest that these methods are suitable for analyzing the crystallization kinetics of the PTT/PEO-MA blends. The PEO-MA component, serving as a nucleation agent in blends, can increase the start crystallization temperatures and accelerate the crystallization rate of the blends. The crystal dimensions are predominantly three-dimensional growths, judged from the Avrami exponent n and the Ozawa exponent m, but the spherulites in blends are much smaller than those in pure PTT. The crystallization active energy suggests that the PEO-MA component can make the PTT component easy to crystallize in blends. The blend has the highest Izod impact strength as PEO-MA content is 3wt.%. Considering both the crystallization kinetic analyses results and the crystal morphology of the blends, the modified Avrami method is believed to be the most useful in reflecting the crystallization of the blends.