聚氯乙烯与氯化聚乙烯共混改性的研究(Ⅱ)

本文用红外光谱法,差示扫描量热法(DSC)研究了氯化聚乙烯(CPE)的链结构性能及其对聚氯乙烯(PVC)改性的影响·用动态力学分析法(DMA)研究了PVC/CPE共混物的动态力学行为,表明CPE,PVC为部分相容两相体系。同时,用透射电子显微镜(TEM)观察了CPE在PVC/CPE共混物中的分布形态。当CPE在PVC/CPE共混物中形成比较完善的网络结构时,共混物具有更好的冲击性能。     

共混方法对聚氯乙烯/聚丙撑碳酸酯相容性影响

本文分别用溶液法和熔融法制得聚氯乙烯（PVC）与聚丙撑碳酸酯（PPC）共混试样，用DSC证明PVC／PPC共混物不相容，但它们不相容的程度受分子量、共混比例等因素的影响，并根据玻璃化转变温度（Tg）计算出溶液共混试样PPC富相中PVC的重量百分含量。NBR／PPC弹性体作偶联剂对PVC／PPC共混体系具有较好的增容作用，共混物中PPC的用量及分子量对共混体系性能有一定的影响。     

相容剂对PP/POE共混体系脆韧转变行为的影响

采用熔融挤出法制备了不同相容剂含量的PP/POE共混体系,测试了不同体系的脆韧转变温度、热性能和力学性能.结果表明,乙烯-丙烯多嵌段共聚物相容剂的加入降低了PP/POE共混物的脆韧转变温度,提高了共混物的韧性.AFM和STEM照片显示相容剂的加入减小了橡胶分散相的临界粒子间距,PP和POE在两相界面结合处相互扩散或渗透,实现了POE弹性体在PP树脂中合适的尺度分布以及良好的形态分散.当相容剂含量达到10％时,POE分散相尺寸细小均匀,分散相粒子粒径为0.54μm,粒子间距为0.1 μm,PP结晶链段更多地插入到弹性体内部,弹性体POE分散相形成明显的“硬核-软壳”结构.DSC曲线中结晶峰和熔融峰的变化说明适量的相容剂对于材料结晶度的提高具有一定的促进作用.力学性能测试结果可以看出相容剂的加入在提高材料韧性,降低其脆韧转变温度的同时也保持了材料的刚性性能.     

聚乳酸/乙烯-醋酸乙烯酯共聚物共混物的形态与黏弹行为

熔融共混制备了不同组分比的聚乳酸(PLA)/乙烯-醋酸乙烯酯共聚物(EVA)共混物,采用扫描电子显微镜(SEM)、溶剂选择性蚀刻和旋转流变仪研究了共混物不相容的相形态及其黏弹响应.研究结果表明,PLA/EVA共混物为典型的热力学不相容体系,两基体组分间的界面张力约为2.2 mN/m;因此随组分比的不同,共混物表现出"海-岛"分散和双连续的不相容相形态;体系中EVA的相反转浓度约为50 wt%～60 wt%,这与黏性模型对相反点预测的结果一致;与双连续相形态的体系相比,乳液模型能够更好的描述具有"海-岛"分散形态的体系的线性黏弹响应,共混体系相对较宽的相反转区域主要源于两组分间较大的弹性比以及EVA自身的屈服行为.     

硬质PVC/ACR共混体系的增韧机理研究

通过TEM、SEM等方法研究了不同结构丙烯酸酯类抗冲改性剂（ACR）对聚氯乙烯（PVC／ACR共混体系形态结构的影响,对ACR增韧硬质PVC的机理作了探讨,当PVC中含有8phr以上完善核壳结构的ACR时,在共混体系能形成网络结构,这一结构在受冲击时产生多重银纹,并实现银纹的纯化,在PVC／ACR共混体系的增韧机理中占主导地位,同时,ACR诱发PVC产生剪切形变也是提高其增韧效果的因素。     

用于观察橡胶改性聚氯乙烯结构的制样方法——氯磺酸-重金属染色法

<正> 使用丁腈橡胶(NBR),氯化聚乙烯(CPE)、乙烯-醋酸乙烯酯共聚物(EVA)、甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物(MBS),丙烯酸酯弹性体(ACR)等材料,可以改善聚氯乙烯(PVC)的抗冲击性能。由于PVC树脂由数种结构层次不同的微粒组成,橡胶改性PVC的性能依赖于加工条件及体系的相结构。观察改性PVC的相结构是研     

SAN共聚物组成对PVC/ABS共混物相容性的影响

采用乳液聚合技术通过改变共聚单体的投料比(St/AN)合成了一系列不同AN结合量的ABS接枝共聚物粉料和SAN共聚物.将其与聚氯乙烯(PVC)和邻苯二甲酸二辛酯(DOP)熔融共混分别制得了PVC/ABS、PVC/SAN、PVC/ABS/DOP和PVC/SAN/DOP共混物,利用SEM、TEM和动态力学粘弹谱仪(DMA)对共混物的相容性和相结构进行了表征.结果发现,在PVC/ABS共混体系中,尽管改变接枝SAN共聚物的AN结合量,PVC和SAN共聚物均为不相容体系;在该共混物中引入增塑剂DOP后,虽然当SAN共聚物AN结合量小于23.4 wt%时,共混物在室温以上只存在一个tanδ峰,但形态结构研究结果表明共混物仍为不相容体系,共混物的相区尺寸明显地依赖于SAN共聚物中的AN结合量,当AN结合量为23.4 wt%时相区尺寸最小.     

ICP-AES法快速分析聚氯乙烯中复合热稳定剂

聚氯乙烯（PVC）的热稳定性较差，在加工过程中必须通过添加2％～4％热稳定剂才能有效地阻止其热降解。工业上广泛应用铅、镉、钡、钙、锌的硬脂酸盐或油酸盐等的复合物作为PVC的复合热稳定剂，通常是二元或三元复合体系，如铅钡、镉钡、镉钡锌、钙锌体系等，由于体系内组分之间有协同热稳定性，不仅使PVC加工时期的色泽好，而且有非常好的长期稳定性。     

强紫外光作用下PVC/增韧剂体系结构与性能的演变

通过UV, FTIR, DSC及力学性能和色差的测试分析, 实时追踪了在紫外光老化过程中, 聚氯乙烯/氯化聚乙烯(PVC/CPE), 聚氯乙烯/丙烯酸酯类共聚物(PVC/ACR)及聚氯乙烯/丙烯腈-丁二烯苯乙烯共聚物(PVC/ABS)体系的微观结构和宏观性能的演变过程. 结果表明, 在光老化过程中, ACR和CPE对PVC脱HCl生成共轭双键反应、氧化降解反应、交联反应及玻璃化转变温度(T_g)的变化等均有抑制作用, 而ABS则对这些反应起促进作用. 在宏观上表现为ACR和CPE的加入能提高体系的色泽稳定性, 体系的力学性能保持率较高. 而ABS的作用相反.     

iPS—b—iPP共聚物对iPS／iPP共混物的性能和形态影响的研究

报道了苯乙烯－丙烯等规嵌段共聚物增溶作用及ｉＰＳ－ｂ－ｉＰＰ／ｉＰＳ／ｉＰＰ三组分共混体系微观形态和力学性能的研究结果。ｉＰＳ－ｂ－ｉＰＰ的加入明显地改善了ｉＰＳ／ｉＰＰ二组分共混物的力学性能；共聚物含量超过１５％时，三组分共混物的抗冲击强度超过ＨＩＰＳ的抗冲击强度，并具有较高的耐热性。ＳＥＭ结果表明，ｉＰＳ－ｂ－ｉＰＰ在ｉＰＳ／ｉＰＰ共混中起到了相分散和相间“偶联”作用，并降低了共混体系的微相尺     

纳米级CaCO_3粒子与弹性体CPE微粒同时增韧PVC的研究

研究了平均粒径为 30nm的超细级纳米CaCO3 与氯化聚乙烯 (CPE)对聚氯乙烯 (PVC)共混体系二元协同增韧效应及机制 .结果表明 ,当共混体系中有一定量的CPE时 ,纳米CaCO3 的加入可以明显地提高共混物的韧性 ,而不降低共混物的强度和刚性 .纳米CaCO3 在PVC基体中达到了纳米级的分散 .当纳米CaCO3 的用量为 8份 (质量 )时 ,PVC CPE 纳米CaCO3 共混物的冲击断面产生了大量的有规则的网丝状结构 ,共混物的缺口冲击强度达到 81 1kJ m2 ,比不加纳米CaCO3 的共混体系高 7 3倍 .CPE的加入对共混体系的加工流动性能无影响 ,纳米CaCO3 的加入使共混体系的加工流动性能变差     

固相法氯化聚乙烯对PVC／LLDPE共混体系性能和形态的影响

采用固相法氯化聚乙烯（ＣＰＥ）对聚氯乙烯／线型低密度聚乙烯（ＰＶＣ／ＬＬＤＰＥ）共混体系进行增容改性。扫描电子显微镜、透射电子显微镜、动态力学分析和力学性能测试结果表明，ＣＰＥ对ＰＶＣ／ＬＬＤＰＥ共混体系具有很好的增容作用。     

Development and characterization of reactive extruded PVC/polyacrylate blends

This paper describes a method to obtain polymer blends by the absorption of a liquid solution of monomer, initiator, and a crosslinking agent in suspension type porous poly(vinyl chloride) (PVC) particles, forming a dry blend. These PVC/monomer dry blends are reactively polymerized in a twin‐screw extruder to obtain the in situ polymerization in a melt state of various blends: PVC/poly(methyl methacrylate) (PVC/PMMA), PVC/poly(vinyl acetate) (PVC/PVAc), PVC/poly(butyl acrylate) (PVC/PBA) and PVC/poly(ethylhexyl acrylate) (PVC/PEHA). Physical PVC/PMMA blends were produced, and the properties of those blends are compared to reactive blends of similar compositions. Owing to the high polymerization temperature (180°C), the polymers formed in this reactive polymerization process have low molecular weight. These short polymer chains plasticize the PVC phase reducing the melt viscosity, glass transition and the static modulus. Reactive blends of PVC/PMMA and PVC/PVAc are more compatible than the reactive PVC/PBA and PVC/PEHA blends. Reactive PVC/PMMA and PVC/PVAc blends are transparent, form single phase morphology, have single glass transition temperature (T_g), and show mechanical properties that are not inferior than that of neat PVC. Reactive PVC/PBA and PVC/PEHA blends are incompatible and two discrete phases are observed in each blend. However, those blends exhibit single glass transition owing to low content of the dispersed phase particles, which is probably too low to be detected by dynamic mechanical thermal analysis (DMTA) as a separate T_g value. The reactive PVC/PEHA show exceptional high elongation at break (～90%) owing to energy absorption optimized at this dispersed particle size (0.2–0.8 µm). Copyright © 2005 John Wiley & Sons, Ltd.     

Morphology and properties of poly(vinyl chloride)–poly(butadiene-co-acrylonitrile) blends

The objective of this research was to study the structure-property relationships of two poly(vinyl chloride) (PVC)–poly(butadiene-co-acrylonitrile) (BAN) blends which exhibit differences in blend compatibility. Studies were carried out utilizing differential scanning calorimetry, dynamic mechanical testing, stress–strain, transmission electron microscopy (TEM), and infrared dichroism experiments at different temperatures. The BAN 31/PVC (BAN containing 31% acrylonitrile) system is considered to be nearly compatible as evidenced by T_g shifts, stress–strain results, orientation characteristics, and TEM micrographs. Similar experiments indicate that the BAN 44/PVC system is incompatible, and contains a mixed phase of BAN 44-PVC and a pure BAN 44 phase. The extent of heterogeneity in the compatible BAN 31/PVC system, however, plays an important role in the orientation characteristics of the blends.     

High‐efficiency impact modifier prepared by coagulation emulsion polymerization through internal voiding toughening mechanism

This paper was an application of our previous study on particle coagulation mechanism (Colloid Polym Sci 291: 2385‐2398, 2013), and the effect of coagulation particle of acrylic impact modifiers (ACR) on polymer blend properties was investigated. The compatibility was relevant with the properties of shell phase rather than the structure of core phase. The rubber content was found to be the main influencing factor for toughening when rubber content less than 5%. However, when it reached to 7%, the dispersion of rubber became the primary parameter to dominate the toughness. The highest impact strength of poly(vinyl chloride) (PVC) toughened by coagulation particles was 1656 J/m, nearly 56 times than pure PVC, whereas only 45 times was reached when toughening by traditional ACR prepared by seeded emulsion polymerization; moreover, the brittle–ductile transition happened in advanced of 2 phr at ACR content. Scanning electron microscopy results showed that the shear yielding of the matrix and rubber cavitation were the major toughening mechanisms. Furthermore, the high performance of blend responsible for coagulation particles was discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Remarkably improved toughness and thermal stability of poly (vinyl chloride) (PVC)/poly (α-methylstyrene-acrylonitrile) (α-MSAN) blend with the assistance of two impact modifiers

The key drawback of impact modifier-toughened polymer is that the improved toughness is accompanied by loss in stiffness. Surprisingly, poly (vinyl chloride) (PVC)/poly (α-methylstyrene-acrylonitrile) (α-MSAN) blend was toughened without loss in stiffness by simply combining two impact modifiers-chlorinated polyethylene (CPE) and acrylic resin (ACR). The prepared blend's impact strength was 3.0 times higher than PVC/α-MSAN/CPE blend and 18.6 times higher than pure PVC/α-MSAN blend. An impressive thermal stabilizing effect was also achieved when CPE and ACR were combined. The improved toughness could be attributed to the overlap of the stress field between different impact modifiers, which help to form the continuum percolation of stress volume under impact loading.     

聚氯乙烯－丁腈橡胶－氯丁橡胶三元共混物的研究

测定了聚氯乙烯（ＰＶＣ）－丁腈橡胶（ＮＢＲ－２９）－氯丁橡胶（ＣＲ）三元共混物的冲击性能和应力－应变行为，用动态力学分析、扫描电镜和透射电镜研究了共混物的相容性和形态结构，结果表明，ＮＢＲ－２９对ＰＶＣ，ＣＲ有良好的增容作用，三元共混物是部分相容的二相体系，具有良好的抗冲击性能。     

Poly (vinyl chloride)/poly (α‐methylstyrene–acrylonitrile)/acrylic resin ternary blends with enhanced toughness and heat resistance

In this study, tough and high heat‐resistant poly (vinyl chloride) (PVC)/poly (α‐methylstyrene–acrylonitrile) (α‐MSAN) blends (70/30) containing acrylic resin (ACR) as a toughening modifier was prepared. With the addition of ACR, heat distortion temperature increased slightly, which corresponded with the increase in glass transition temperature measured by differential scanning calorimetry and dynamic mechanical thermal analysis. Thermogravimetric analysis showed that addition of ACR improved the thermal stability. With regard to mechanical properties, tough behavior was observed combined with the decrease in tensile strength and flexural strength. A brittle‐ductile transition (BDT) in impact strength was found when ACR content increased from 8 to 10 phr. The impact strength was increased by 34.8 times with the addition of 15 phr ACR. The morphology correlated well with BDT in impact strength. It was also suggested from the morphology that microvoids and shear yielding were the major toughening mechanisms for the ternary blends. Our present study offers insight on the modification of PVC, since combination of α‐MSAN and ACR improves the toughness and heat resistance of pure PVC simultaneously. Copyright © 2011 John Wiley & Sons, Ltd.     

PS-b-PMMA对PVC/SBS共混体系界面结构的影响

在两种不相容的聚合物组成的共混体系中加入增容剂，可以显著提高共混体系的力学性能．目前的理论解释是嵌段共聚物在不相容的聚合物间形成界面层，通过降低组分间的界面张力、增强界面粘接力达到增容目的［‘－‘1．但是这一假设缺乏直接的实验证据．本文利用透射电子显微镜，