辊速辊温对高密度聚乙烯拉伸微孔膜及其片晶结构的影响

采用熔融挤出片材—退火—冷拉伸—热拉伸—热定形的方法来制备高密度聚乙烯(HDPE)微孔膜,利用FTIR、SEM和DSC等测试方法来研究辊速辊温对HDPE拉伸微孔膜及其片晶结构的影响.研究结果表明,所选树脂的分子量、分子量分布以及弛豫时间能够满足现有加工条件,形成片晶取向度较高的预制膜;在相同辊温下,随辊速增加,退火前预...     

原位小角X射线散射研究热拉工艺对熔融拉伸法制备的聚丙烯微孔膜结构的影响

采用原位小角X射线散射和扫描电子显微镜研究了热拉过程中,拉伸比和拉伸温度对熔融拉伸法制备的聚丙烯微孔膜晶体和孔洞结构的影响.研究结果表明,冷拉、热定型过程中片晶簇被分离开,其内部结构在热拉过程中不发生分离等变形;随着热拉拉伸比的增加,片晶簇间架桥长度不断增大;与冷拉、热定型样品相比,热拉后的微孔膜架桥沿垂直于拉伸方向具有较好的周期性.不同的拉伸温度结果表明,架桥长度随拉伸温度升高而增加;温度过高时架桥会发生熔融.     

聚丙烯分子量对热致相分离制备微孔膜的影响

通过对等规聚丙烯与邻苯二甲酸二戊酯体系的相分离过程进行研究,绘制了3种分子量等规聚丙烯与邻苯二甲酸二戊酯体系的相图.研究结果表明,聚丙烯分子量的增大导致聚合物单个分子占据的晶格数Np增加,总分子数减少,使混合熵对混合自由能的贡献降低,因此浊点曲线向高温方向移动,而结晶曲线基本不变.聚丙烯分子量的增大延长了聚合物贫相分散液滴的生长时间、增加了聚合物富相黏度和过冷度.聚丙烯分子量变化不仅改变了微孔尺寸,而且改变了微孔结构.在相同淬冷条件下,微孔平均尺寸的变化趋势是贫相分散液滴的生长时间、聚合物富相黏度和过冷度3种因素共同作用的结果.     

热致相分离聚丙烯微孔膜

对聚丙烯－稀释剂体系热致相分离过程制备聚丙烯微孔膜的意义、原理、过程及研究现状进行了评述。     

聚丙烯中空纤维膜的微孔结构的控制

通过熔纺／冷拉伸法制备了微孔聚丙烯中空纤维膜。研究了工艺条件对微孔聚丙烯中空纤维膜的微孔结构与性能的影响。结果表明：随着纺丝温度的下降或熔体拉伸比的提高，最大可几孔径及孔隙率增大；熔纺中冷却风速提高，最大可几孔径及孔隙率较大；温度低于110℃时，热处理对最大可几孔径及孔隙率的影响较小，在120－130℃时，随着热处理温度的增加，最大孔径及孔隙率有明显增加的趋势；随着初纺中空纤维拉伸倍数的增加，孔隙率先增加而后下降。     

聚丙烯微孔膜的等离子接枝

在新型聚丙烯微孔膜上的低温等离子接枝饱和的非离子型表面活性剂，使对水的接触角由108°降低到48°。提出了自由基接枝机理。研究了接枝过程主要参数对接枝率的影响，证实了存在接枝和刻蚀竞争机制。     

应力场下固—液相分离制备微孔聚丙烯中空纤维膜

将聚丙烯和石蜡油的混合物熔融挤出,使之在较高的应力场下冷却和相分离,得到了弹性聚丙烯中空纤维。这种部分结晶的弹性纤维可能具有平行排列的片晶结构,石蜡油存在于片晶之间。将石蜡油提取掉后稍加拉伸即可得到透气性很好的微孔中空纤维渗透膜。     

聚丙烯微孔膜的等离子体接枝聚合改性

利用拉伸时的晶型转变致孔特性,从β晶相聚丙烯经单向或双向拉伸制得了新型聚丙烯微孔膜、用等离子体接枝聚合技术接上了亲水性聚合物如聚丙烯酸、聚丙烯腈等。研究了等离子体处理时间、单体性质对得到的亲水膜的亲水性、离子/溶质渗透性的影响。发现接枝聚丙烯酸的双向拉伸膜对Na~+、Mg~(++),尿素有较大的渗透性,并具有优良的形状稳定性。     

熔融拉伸法制备聚丙烯微孔膜成孔机理的原位小角X射线散射研究

采用熔融拉伸法制备聚丙烯微孔膜,在避免冷拉会自然回缩和热处理后样品需降温检测等因素对冷拉伸样品影响的情况下,在线研究了冷拉、热定型、热拉过程中样品结构变化.原位小角X射线散射检测与扫描电子显微镜、示差扫描量热仪结合深入研究了不同的冷拉拉伸比对微孔膜片晶和孔洞结构的影响.结果表明不同的冷拉伸比其成孔机理不同,冷拉15%,仅拉伸方向长周期发生微弱的变化,其成孔机理是冷拉产生缺陷,热拉成孔;冷拉30%拉伸主要是将薄弱片晶拉伸转变为不稳定的架桥,热定型阶段部分架桥断裂,竖直方向上产生明显的Streak信号;冷拉40%拉伸方向信号显示实际片晶长周期的增长率小于宏观应变,部分骨架片晶在冷拉阶段已被拉伸破坏成孔.随着冷拉拉伸比增大架桥长度变短,孔径减小,30%是制备微孔膜较合适的冷拉拉伸比.     

聚丙烯微孔膜表面的等离子体接枝

通过氢气氛等离子体处理，在聚丙烯微孔膜表面接枝了聚丙烯酸，改善了膜表面的亲水性。接枝率与等离子体放电功率、放电时间和溶液浓度有关，微孔膜内外表面及不同位置接枝效率有差别。接枝后微也膜的表面孔径减少了。     

SURFACE MODIFICATION OF POLYPROPYLENE MICROPOROUS MEMBRANES BY THE ADSORPTION OF NON-IONIC SURFACTANTS

Surface modification by physical adsorption of a series of non-ionic surfactants including Tween 20, Tween 40, Tween 60, Tween 80 and Tween 85, was accomplished on polypropylene microporous hollow fiber and flat membranes. The adsorption curve of the membrane surface was analyzed by weight measurements and the typical results showed a twoplatform character similarly. Differences in the degree and curve shape of adsorption resulting from such factors as concentration, temperature, as well as water cleaning time were observed for Tween 85 among other Tweens. Attenuated total reflection - Fourier transform infrared spectroscopy analysis and field emission scanning electron microscopy observation showed that the adsorption of Tween on polypropylene microporous membrane （PPMM） is effective and occurs mainly in the pores of PPMMs at low adsorption amount, and on the membrane surface also at high adsorption value.     

EFFECT OF MOLECULAR WEIGHT OF PDMS ON MORPHOLOGY AND MECHANICAL PROPERTIES OF PP/PDMS BLENDS

A series of polydimethylsiloxane (PDMS) with varied molecular weights (M_w=3×10~6,1×10~6 and 0.5×10~6) were melt blended with PP to investigate the effect of PDMS molecular weight (MW) on the morphology and mechanical properties of PP/PDMS blends.Scanning electron microscopic (SEM) examination showed that the size of PDMS domains was dependent on the MW of PDMS.It was found that the lower the value of PDMS MW,the better dispersion of the PDMS domains in the PP matrix.Tensile and Izod impact tests reveale...     

EFFECT OF MOLECULAR WEIGHT OF PDMS ON MORPHOLOGY AND MECHANICAL PROPERTIES OF PP/PDMS BLENDS

 A series of polydimethylsiloxane (PDMS) with varied molecular weights (Mw = 3  106, 1  106 and 0.5  106) were melt blended with PP to investigate the effect of PDMS molecular weight (MW) on the morphology and mechanical properties of PP/PDMS blends. Scanning electron microscopic (SEM) examination showed that the size of PDMS domains was dependent on the MW of PDMS. It was found that the lower the value of PDMS MW, the better dispersion of the PDMS domains in the PP matrix. Tensile and Izod impact tests revealed that the addition of PDMS with lower MW would lead to a more significant increase in impact strength of the blends compared with the blends with higher MW ones, while the influence of the molecular weight on tensile strengths of the blends was relatively small in the MW range studied. Differential scanning calorimetry (DSC) results also showed that the crystallization temperature of PP was increased with decreasing PDMS MW, indicating a better nucleation capability of lower MW of PDMS. Melting flow rate (MFR) measurements indicated that the processibility of PP could be enhanced by adding PDMS, and again the lower MW PDMS resulted in better data. Our work demonstrates that not only the processibility but also the mechanical properties of PP could be enhanced to a more significant degree by using low MW PDMS than the higher ones.     

分子量对聚丙烯等温结晶的影响

<正> 在高聚物结晶动力学的研究中,分子量对结晶速率的影响是一个有实际意义和理论兴趣的研究课题,由于聚烯烃可以得到分子量变化范围相当宽(MW从10~3到10~6)的试样,因而它是研究结晶速率分子量依赖性较合适的对象,其中研究最多的是聚乙烯和聚丙烯。从前入的研究报道看来,影响聚丙烯结晶速率的因素比聚乙烯要复杂。除了聚丙烯可生成多种晶型结构,会影响其结晶速率以外,用不同聚合方法制备的试样,由于其链结     

分子量对聚丙烯银纹形态的影响

<正> 聚合物在拉伸状态下发生脆性破坏和银纹的形成与发展有着密切联系,银纹与其它局部塑性形变的本质区别在于银纹中存在的微纤,它将两个银纹面连接起来,并能在其中传递载荷,在拉伸应力的作用下,银纹微纤断裂发展成为裂纹,最后导致材料破坏。 最近十几年里,对以PS、PMMA、PC为代表的非晶态聚合物中的银纹化现象作了比较广泛、深入的研究(如不同热历史、不同的银纹化环境等),对银纹的引发、增长、微纤的断裂等现象进行了大量的观察,也提出了一些理论模型来解释银纹化的全过程,这是因为非晶态聚合物具有相对简单的三维空间结构。     

硬弹性聚丙烯晶相和非晶相分子链取向的研究

本文用力学-振动光谱研究了硬弹性聚丙烯(HEPP)晶区和非晶区分子链在拉伸时取向的变化.我们发现在红外光谱中,1130—1190cm~(-1)波数范围内存在着三个峰,其中1167cm~(-1)处的峰是与结晶相长螺旋分子链相关的构象谱带,其谱带的强弱变化是与998cm~(-1)结晶谱带在拉伸时的变化趋势一致的.1159cm~(-1)谱带能够被归属于无定形谱带.而1152cm~(-1)处的峰也许是与短螺旋分子链构象谱带相关的.我们用计算机的二次微分、解卷积以及分峰程序测定了拉伸时HEPP晶区和非晶区分子链的取向函数,结果发现HEPP无定形分子链取向随拉伸比增加而增加,而晶区分子链的取向随拉伸比的增加先下降,直至拉伸比为1.5(第二次屈服点)后才逐渐增加.     

THE EFFECT OF EC ON ORIENTATION AND RELAXATION OF PP OBTAINED VIA DYNAMIC PACKING INJECTION MOLDING

As a long term project aiming at engineering plastics based on polypropylene (PP), in this work, we report the effect of ethylene-cellulose (EC) on the orientation and relaxation of PP obtained via dynamic packing injection molding (DPIM). 2d-WAXD results showed that PP with a highly oriented structure and a shish-kebab structure were achieved by DIPM, leading to an increase of tensile strength from 35.0MPa to 48.6MPa. The degree of orientation of PP was increased by adding only 1% of EC, resulting in a further increase of tensile strength from 48.6MPa to 53.8MPa. Shish was found to exist not only in the oriented layer but also in the core of the sample after adding EC, as evidenced by DSC result.This was understood as due to the overall decrease of viscosity by the addition of EC, thus an increasing of shear rate. Higher shear rate can favor the orientation of molecules and continuous growth of shish structure, resulting in a change of shish distribution along the sample thickness. On the other hand, the relaxation mode of shish in the melt recrystallization of PP is also greatly affected by the presence of EC. A retarded relaxation of PP macromolecules was seen.Even more, SEM results showed that EC could form the short fibers in PP matrix along the shear flow direction. Compared with the morphology obtained by conventional injection molding, a much better dispersion and easy break-up of EC in PP matrix were observed for samples obtained by dynamic packing injection molding.     

高分子量聚乙烯醇增强冰的研究

以本体光聚合法制备的高分子量聚乙烯醇(HMWPVA)为增强剂,考察了增强冰的力学性能.当HMWPVA的浓度为3%(质量分数)时,增强冰的拉伸强度、断裂伸长率、压缩强度和压缩模量分别为普通冰的11.7,3.5,2.3和2.1倍.对比试验发现PVA分子量对冰的拉伸性能影响较大,对冰的压缩性能影响较小.此外,在室温29℃时纯冰的融化时间为5 min,而4%HMWPVA增强冰的融化时间长达240 min.