聚乙烯共混体系中的共结晶行为及对性能的影响

选用HDPE和LLDPE为原料进行熔融共混,通过差示扫描量热(DSC)测试、连续自成核退火(SSA)热分级法探究线型与支化聚乙烯分子的共结晶行为,尤其是采用SSA热分级法剖析了形成共晶的分子链的结构特征,并在此基础上研究共结晶对共混物力学性能的影响。DSC结果表明,HDPE与LLDPE具有较好的相容性且HDPE在共混物结晶过程中具有成核作用。SSA测试显示,HDPE/LLDPE共混物的结晶行为依赖于LLDPE组分的支链分布,只有当LLDPE的亚甲基序列长度与HDPE的链段相互匹配时才会形成共晶。共混物的屈服强度与共混体系的结晶度以及晶片厚度有关。屈服强度与自然拉伸比均随LLDPE质量分数的增加而减小。     

PP/POE共混物的热行为与晶态结构

采用双螺杆挤出机熔融共混制备了不同组成的聚丙烯(PP)/乙烯-辛烯弹性体(POE)共混物,利用差示扫描量热仪、偏光显微镜和广角X射线衍射系统研究了共混物的热行为与晶态结构。结果表明PP与POE之间具有一定的相容性,POE的异相成核作用提高了共混物中PP的结晶温度和结晶速率,有效地诱导β晶型PP的形成,增大了共混物中α晶型和β晶型PP的晶面表观厚度。另一方面,由于POE与PP之间存在较强的相互作用,POE大分子链使PP分子链的扩散和堆积受阻,从而导致PP/POE共混物总结晶度的降低。     

聚丙烯/尼龙弹性体复合体系相容性的研究

采用尼龙弹性体(PAE)对PP进行增韧增强改性,同时添加马来酸酐接枝聚丙烯(MPP)来改善PP与PAE的界面相容性。利用扫描电镜(SEM)、差示扫描量热仪(DSC)等手段及力学性能测试,比较研究了MPP对共混物结晶温度及力学性能的影响。结果表明,PAE适用于PP的增韧改性,且增韧效果取决于三元共混体系中MPP的含量;当所含MPP的质量分数达到3%,共混材料界面相容性好,共混物韧性高。     

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。     

光缆护套料用高密度聚乙烯/线型低密度聚乙烯的界面作用与流变行为

采用熔融共混法制备了光缆护套料用高密度聚乙烯(HDPE)/线型低密度聚乙烯(LLDPE)与HDPE/茂金属线型低密度聚乙烯(m-LLDPE)2种共混物,讨论了共混物HDPE/LLDPE和HDPE/m-LLDPE及中密度聚乙烯(MDPE)与铝塑带之间的热合强度,并研究了共混物的力学性能、松弛行为及组分间的相容性。研究结果表明,HDPE/LLDPE(7∶3)共混物与铝塑带热合强度最高(27.2 N/cm);熔融状态下,低频区HDPE/LLDPE的lgG′-lgω与线性偏离,且松弛指数(λ)随HDPE含量增加先减小后增大,表明分子链缠结先增强再减弱,为非均相体系;HDPE/LLDPE只表现出1个熔融峰,表明共混物组分具有良好相容性;因分子界面多重叠,HDPE/LLDPE(7∶3)具有更小分散相尺寸(2.74 nm)与更高界面层厚度(1.02 nm),组分相容性最好,且与热熔胶乙烯-醋酸乙烯共聚物(EVA)的界面张力最小。可见,采用来源广、价格相对低廉的HDPE与LLDPE共混可实现替代MDPE制备光缆护套料。     

PHB/PLLA共混体系和PHB/PLLA/PEO共混体系冷结晶性的研究

利用DSC研究了聚β-羟基丁酸酯(PHB)与聚乳酸(PLLA)共混物的冷结晶性、相容性和结晶度以及聚氧乙烯(PEO)对PHB/PLLA(质量比为1∶1)共混物冷结晶性、熔融温度和结晶度的影响。结果表明,PHB冷结晶温度及结晶速率不受组分PLLA的影响,而PLLA尽管冷结晶温度不受组分PHB的影响,但其结晶速率随PHB组成增多而变快,共混物结晶度与组分之间的比例相关;PHB与PLLA有一定的相容性,PEO的加入提高了其相容性;同时,PEO的加入,不但显著降低了PHB、PLLA的冷结晶温度,还增进了共混物组分结晶的完善。     

胍基聚电解质与聚丙烯共混体系的流变性能研究(I)PHGC/PP

以毛细管流变仪研究了不同组成的PHGC／PC共混体系的熔体流变行为,分别讨论了熔体粘度与温度、共聚体系组成之间的关系,并在电镜下观察了共混体系的相态结构,分析了共混体系的相容性对熔体流变行为的影响。结果表明,在实验条件下,PHGC／PP共混体系为切力变稀型流体;PHGC与PP相容性较差,在PP中分散颗粒较大;PHGC含量较低时,熔体粘度有极小值,随着温度和剪切速率的变化,熔体粘度随HGC含量的变化呈现出不同的变化趋势。在PHGC含量为2．5％时,非牛顿指数最大,粘流活化能最小。     

剪切和拉伸流场对动态硫化EPDM/PP的力学性能与结晶结构的影响

利用以拉伸流场为主的叶片挤出机(VE)和以剪切流场为主的双螺杆挤出机(TSE)分别制备了不同组分比的动态硫化三元乙丙橡胶/聚丙烯(EPDM/PP)热塑性弹性体。通过对2种流场作用下共混物的力学性能、结晶熔融行为以及晶体形貌和晶体结构的对比分析,研究了拉伸流场对动态硫化EPDM/PP结构与性能的影响。结果表明,与双螺杆挤出机相比,由于拉伸流场更好的分散混合效果,EPDM/PP热塑性弹性体中的PP相能在较低温度结晶,共混物中PP相的晶体尺寸更小,分布更均匀,EPDM相与PP相界面结合更好,共混物的力学性能得到了显著提高;拉伸流场对EPDM/PP热塑性弹性体中PP相的晶格结构无影响,但对PP的结晶度影响较大。     

PVA／P（VA—VP）共混物的动态力学性能

用粘弹谱法(DVE)研究了醋酸乙烯酯和乙烯基吡咯烷酮共聚物的水解物P(VA-VP)和聚乙烯醇(PVA)共混体系的动态力学行为。共混物的阻尼松弛谱(tgδ)表明了共混体系的相容性随着组成比的不同而明显不同,一些组成比的共混物不仅存在晶相和非晶相的聚态结构,而且在非晶相态里随着组成比的不同还存在着微观结构不均匀性和相容性的差异。组成比(W_(PVA))为40～60％的共混物其复合模量和tgδ谱表明共混物中PVA的晶相是均匀分散在共容的非晶介质中,因而在室温至约80℃范围内能形成强度比纯PVA更好的有实用意义的功能PVA合金。 选择两种不同组成比的共混物通过改变升温速率和作用力频率的试验表明,随着升温速率的下降,非晶部分的相容性增大而晶相部分的结晶度增加;作用力频率的下降导致结晶度提高和T_8真升高。     

多单体熔融接枝PP增容PP/PVC共混体系的力学和流变性能研究

合成了一种新型的多单体接枝物PP－g-(St-co-MMA),研究了其对PP／PVC共混体系的增容作用。讨论了接枝物用量对共混物力学性能和流变行为的影响，并通过扫描电镜（SEM）对共混物的亚微观相结构进行了分析。结果表明，该接枝物对PP／PVC共混体系有较好的增容效果，材料的力学性能在接枝物用量为6份时出现峰值；加入接枝物能使体系的熔体粘度增加，并且在所研究的温度和压力范围内共混物熔体呈典型的假设性流体特性。     

LLDPE及LLDPE／LDPE在不同条件下的结晶行为

ＤＳＣ的研究表明ＬＬＤＰＥ高分子量线形分子结晶时，短支化链的链节不参与共晶。当ＬＬＤＰＥ／ＬＤＰＥ共混物淬冷或快速结晶时，ＬＬＤＰＥ中的线形分子可与ＬＤＰＥ中长支化链的链节产生共晶，其熔融单峰较宽，峰位随ＬＬＤＰＥ含量增加而稍向高温移动。     

Crystallization of partially miscible linear low-density polyethylene/poly(ethylene-co-vinylacetate) blends

Miscibility and crystallization of linear low-density polyethylene (LLDPE)/poly(ethylene-co-vinylacetate) (EVA) blends were investigated by optical microscopy (OM) and differential scanning calorimetry (DSC). It was found that there existed liquid–liquid phase separation (LLPS) below 220 °C over the whole composition. However, the depression in the crystallization temperature, melting temperature and equilibrium melting temperature of LLDPE all indicated that this polymer pair was partially miscible. The crystallization and melting behavior of LLDPE were determined by the dilute effect of non-crystalline EVA and the probable co-crystallization of parts of EVA chains with LLDPE chains. The crystallization and melting behavior of EVA was determined by the competence between a nucleation effect of LLDPE crystals and partial miscibility between this polymer pair, which was different from that of LLDPE.     

马来酸酐混合单体改性PP/PS共混物的结晶与动态力学性能

用熔融法制备了马来酸酐（MAH）及其与苯乙烯（St）混合单体改性PP／PS共混物,以及MAH、St改性聚丙烯（原住形成PP／PS共混物）。用DSC、DMA和FT—IR研究了改性共混物的结晶与熔融行为、动态力学性能和接枝产物。结果表明,MAH加入对PP／PS共混物中PP的结晶温度影响不大,但其与St混合单体对共混物中PP的结晶温度影响明显,原位生成PP／PS的结晶温度也有较大提高。改性对共混物中PP的熔融温度影响不大,但熔融峰形变化明显。改性PP／PS共混物具有高的E′和E″强度。     

Polycarbonate-linear low density polyethylene blends: Thermal and dynamic-mechanical properties

Blends of polycarbonate (PC) and linear low density polyethylene (LLDPE) of different compositions, in the form of slabs obtained by melt extrusion, have been examined by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA).DSC measurements show that the melting, crystallization and glass transition temperatures of the two polymeric components in the blends are slightly affected by the composition. On the contrary, large differences are observed in the melting behaviour of layers cut at various depths, parallel to the slab surfaces of samples. This supports the occurrence of different crystal morphologies and distribution of the two components within the samples. The study of the crystallization kinetics from the melt blends shows that the crystallization processes of LLDPE are affected by the presence of PC.The dynamic mechanical analysis indicates that modulus, transitions and relaxational behaviour of the polymer components are scarcely affected by the composition. Some variations of the damping factor have been interpreted as due to the phase heterogeneity of the system, arising from the processing conditions and rheological behaviour of the blends.     

Toughening effect of maleic anhydride grafted linear low density polyethylene on linear low density polyethylene

The blend of linear low density polyethylene (LLDPE) and maleic-anhydride grafted LLDPE with the grafting degree of 1.3% and the gel content of 27.0% (designated as LLDPE/MA-PE) was melt-compounded. Their thermal, rheological, and mechanical properties were studied. The crystallization temperature and crystallization rate of LLDPE/MA-PE blends increase due to the nucleation of MA-PE, their crystallinity is between those of LLDPE and MA-PE due to the balance between the nucleation of MA-PE and simultaneously produced more defects. The addition of MA-PE increases the apparent viscosity of blend melts, but the shear-sensitivity of blends provides them with melting processing. Interestingly, the lamellar crystallites induced by MA-PE decrease the tensile yielding strength of LLDPE/MA-PE blends. During the impact fracture, the formation of oriented crystalline lamellae parallel to the crack front and perpendicular to the crack flank, leads to the deformation and microstriations in LLDPE/MA-PE blends. Subsequently, toughness of LLDPE/MA-PE blends is improved.     

DSC法快速评定阻燃剂对聚丙烯结晶及力学性能的影响

利用DSC法对几种典型的阻燃聚丙烯体系进行了研究,得到了一种快速评定阻燃剂对PP结晶性能影响的方法。结果表明,PP的结晶行为及各阻燃剂对PP结晶行为的影响,可在这些体系非等温结晶的DSC放热峰的峰形、峰位及峰的面积上得到很好体现。另外,也研究了这些体系由于阻燃剂的加入而引起的力学性能的变化。     

咪唑基离子液体[C_(14)mim]Br对LLDPE结构与性能的影响

应用离子液体[C14mim]Br和线型低密度聚乙烯(LLDPE)熔融共混,制备出LLDPE/[C14mim]Br共混物,并对共混物结构与性能进行了表征与测试。结果表明,随着[C14mim]Br在共混物中含量的增加,LLDPE晶粒尺寸变大,而且在相同的降温速率下,[C14mim]Br使LLDPE起始结晶温度提高,表明[C14mim]Br起到了异相成核的作用。[C14mim]Br加入量为2.0 phr时,材料抗静电性能最好,表面电阻为1.8×108Ω。随着[C14mim]Br添加量的增加,材料的熔融指数有增加的趋势,而且材料拉伸强度先增大,后逐渐减小,冲击强度先减小,后逐渐增大,[C14mim]Br起到了反增塑与增塑的作用。     

聚丙烯规整性和分子量对结晶性能的影响

采用等温和非等温差示扫描量热(DSC)法研究了聚丙烯规整性和分子量对其结晶性能的影响。结果表明,采用等温结晶分析,聚丙烯的规整性与其熔点成线性关系。但对于分子量很低或规整性很高的聚丙烯,其熔点和规整性不符合以上线性关系。采用非等温结晶分析,聚丙烯规整性的对数与其熔融焓的对数成线性关系。对乙烯共聚研究结果说明,对高规整性聚丙烯,极少量乙烯共聚也会影响其规整性。     

过氧化物动态硫化EPDM/PP热塑性弹性体的等温结晶行为

通过差示扫描量热分析法详细表征了PP、PP/过氧化物、EPDM/PP及过氧化物动态硫化EPDM/PP(TPV)的等温结晶行为。结果表明,与EPDM的简单共混既降低了PP的结晶速率也降低了PP的结晶度,过氧化物动态硫化后交联的EPDM颗粒作为异相成核剂,能大大提高PP的结晶速率但也严重地降低了PP的结晶度,TPV的Avrami指数为3.5,符合异相成核的三维球型生长方式。X射线衍射结果表明,4组样品的晶体结构完全相同,仍为α型单斜晶体。熔融曲线显示过氧化物/PP及TPV相比PP,在153℃出现额外熔融峰,PP原有的160℃熔融峰逐渐消失而153℃熔融峰强度逐渐增强且体系的结晶度逐渐降低。采用移动窗口二位相关红外对TPV熔融行为进行研究,发现153℃处的熔融峰对应于10个和5个单体单元螺旋序列结构,160℃时对应12个单体单元螺旋序列结构。较低的结晶温度有助于长螺旋序列结构的形成及PP结晶度的提高。     

Use of Differential Scanning Calorimetry (DSC) in the Characterization of EPDM/PP Blends

New polyolefinic thermoplastic elastomers based on the ethylene–propylene-diene monomer (EPDM) and polypropylene (PP) containing an EPDM elastomer of the last generation (Nordel NDR 47130), obtained by polymerization in the gaseous phase with metallocene catalysis, were prepared and characterized. The melting and crystallization behavior of these blends was investigated by differential scanning calorimetry. It is observed that the melting temperature, crystallization temperature, and crystallinity degree increase with an increase of PP loading. The influence of the blend composition on the physico-mechanical characteristics was discussed using statistical processing of the experimental data. Two compatibilizing procedures were utilized to improve the physico-mechanical characteristics of the samples: an addition method using different compatibilizing agents and dynamical vulcanization with three types of crosslinking systems. Significant improvements of the tensile strength and tear strength were noted by dynamic crosslinking, and the best results were obtained using a crosslinking system based on phenolic resin and tin chloride.