COMPATIBILITY OF PVC WITH POLYURETHANES OF DIFFERENT SOFT SEGMENTS

Blends of PVC and polyurethanes with four different soft segments of molecular weight 1000 were prepared and studied by dynamic mechanical and DSC techniques. It was found that the compatibility of PVC with segmented polyurethanes was related to the mixing of PVC molecules and the soft segments of the polyurethanes. Polyester based polyurethanes are more compatible with PVC than polyether based polyurethanes. Solution cast blends of PVC with PCL-polyurethane (1/2/1) exhibit single and narrow glass transition, while the blends with PPO-polyurethane (1/2/1) are completely incompatible. The compatibility was found to decrease with increasing hard segment content for all the polyurethanes used. The methods of blend preparation may change the compatibility of PVC/PU blends through their influence on the mixing or demixing of the hard and soft segments.     

MECHANICAL MODEL FOR TWO-PHASE POLYMER BLEND SYSTEMS WITH THE CHARACTERISTICS OF PHASE INVERSION

For two-phase polymer blend systems, the phase inversion will take place as the blendcomposition is changed. In this paper a mechanical model has been proposed to describe themodulus-composition relation in the phase inversion region. The application of the mechanicalmodel to two polyurethane blend systems has been studied. It was found that the theoreticalprediction for the modulus-composition relation is quite consistent with the experimentalresults. Furthermore, the characteristics of the phase inversion can be determined uniquelyby the parameters involved in the mechanical model.     

聚合物共混物脆韧转变性能研究 V.橡胶粒子的分布对聚氯乙烯/丁腈橡胶共混物韧性刚性关系的影响

聚合物共混物脆韧转变性能研究Ｖ．橡胶粒子的分布对聚氯乙烯／丁腈橡胶共混物韧性刚性关系的影响刘浙辉朱晓光张学东漆宗能（中国科学院化学研究所工程塑料国家重点实验室北京１０００８０）蔡忠龙（香港理工大学应用物理系香港九龙）王佛松（中国科学院北京...     

GAS PERMEATION OF SEGMENTED POLYURETHANES AND THEIR BLENDS WITH PVC

Film specimens of four segmented polyurethanes with different soft segments, namely polycaprolactone, polytetramethylene adipate, polytetramethylene oxide and polypropylene oxide, and their blends with PVC of different compositions were obtained by solution cast. The permeability of these films to O_2, N_2 and H_2 and their density were measured by using gas chromatography and technique of density gradient column. The polyether polyurethanes were found to have higher permeability than the polyester ones due to their low glass transition temperature and /or the low density value. The blends of PVC and polyether polyurethanes, especially the PPO-based polyurethane, are incompatible, and their permeability coefficient-composition dependence has the typical S-shaped curves. PVC is well compatible with the soft segments in its blends with polyester polyurethanes. For these blends the composition dependence of permeability is characterized by a negative deviation from the semilogarithmic additivity rule, and it is possible to prepare blends having T_g 20℃lower than that of PVC, but retaining its low permeability almost unchanged, results were discussed in according with the different approaches for the permeation behavior of compatible and incompatible blends.     

PVC/ACR共混物微观结构与性能

本文研究了聚氯乙烯/丙烯酸酯类共聚物(PVC/ACR)共混物的应力-应变行为和冲击强度对ACR 用量的依赖关系。ACR对 PVC有良好的增韧作用,提高了PVC抗冲击性能。考察了三盐基性硫酸铅和硬脂酸钡-硬脂酸镉稳定剂对共混体系的影响,实验结果说明不同的热稳定体系对ACR改性PVC的效果有差别。动态力学性能测定结果表明PVC/ACR共混物存在两个玻璃化转变温度,证明PVC与ACR不相容性;而两个转变温度随共混物组成改变而变化,说明PVC与ACR之间存在着相互作用,PVC/ACR为部分相容体系。通过透射电子显微镜观察PVC/ACR共混物的微观结构形态表明:PVC与 ACR为两相体系,ACR呈粒状分布在PVC连续相中。但是,采用硬脂酸钡-硬脂酸镉稳定体系时,随着ACR用量增加,ACR的分散形态由粒状分散逐渐形成网络结构形态,与此相对应的共混物具有更好的抗冲击性能。     

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     

聚合物共混物脆韧转变性能研究 Ⅳ橡胶粒子的分布对PVC/NBR共混物脆韧转变的影响

根据作者已建立的准网络形态模型和推导出的基体层厚度计算公式，从实验上研究了橡胶粒子的分布对聚氯乙烯（ＰＶＣ）／丁氰橡胶（ＮＢＲ）共混物脆韧转变的影响．结果表明，不仅无规形态ＰＶＣ／ＮＢＲ共混物存在脆韧转变主曲线，而且准网络形态ＰＶＣ／ＮＢＲ共混物也存在脆韧转变主曲线．但是两条主曲线明显不重合，表明橡胶粒子的分布对ＰＶＣ／ＮＢＲ共混物脆韧转变有显著影响．而且准网络形态ＰＶＣ／ＮＢＲ共混物的临界基体层厚度比无规形态ＰＶＣ／ＮＢＲ共混物的临界基体层厚度大得多，表明准网络形态比无规形态明显有利于增韧．因此临界基体层厚度不仅是基体的特征参数，还是界面粘结和橡胶粒子分布的函数．     

A dielectric study of poly(ethylene-co-vinylacetate)–poly(vinyl chloride) blends. I. Miscibility and phase behavior

Measurements of the complex permittivity were used to study miscibility and phase behavior in blends of poly(vinyl chloride) (PVC) with two random ethylene—vinyl acetate (EVA) copolymers containing 45 and 70 wt % of vinyl acetate. The dielectric β relaxation of the pure polymers and blends was followed as a function of temperature and frequency for different blend compositions and thermal treatments. Blends of EVA 70/PVC were found to be miscible for compositions of about 25% EVA 70 and higher. Blends of lower EVA 70 content showed evidence of two-phase behavior. EVA 45/PVC blends were found to be miscible only at the composition extremes; at intermediate compositions these blends were two-phase, partially miscible. Both blend systems showed lower critical solution temperature behavior. Phase separation studies revealed that in the EVA 45/PVC blends, PVC was capable of diffusing into the higher T_g phase at temperatures below the T_g of the upper phase. In the blends, ion transport losses were significant above the loss peak temperatures, and in the two-phase systems, often obscured the upper temperature loss process. It was shown possible, however, to correct the loss curves for this transport contribution.     

二次电子衬度曲线法研究PVC/MBS共混物断面的分形特征

利用二次电子衬度曲线法测定了聚氯乙烯甲基丙烯酸甲酯丁二烯苯乙烯共聚物(PVCMBS)共混物冲击断面的形貌特征及对应的分形维数值.结果表明,材料的断口或微观结构并不是严格的分形结构,这种自相似性仅存在于一定尺码范围内,不同断面形貌特征所对应的分形维数测量值不同,随着MBS用量增加,PVCMBS共混物缺口冲击强度随满足自相似原理的形貌特征所对应的分形维数值增大而增大.本文从理论上讨论了材料断裂韧性与分形维数的关系.     

聚合物二元共混物拉伸强度混合规则的改进模型

改进了关于聚合物二元共混物拉伸强度混合规则的模型 ,保留了原模型中分别表征共混物界面和相结构对共混物拉伸强度产生影响的两个因子F和M .用此模型处理了三个共混体系的拉伸强度数据 ,反算出共混体系的界面强度因子F和相结构强度因子M ,结果表明 ,该改进模型的预测值与实验结果相符程度与原式几无差别 ,但使F和M的物理意义更为明确、合理 ,其相关系数也有所增大     

聚ε-己内酯/聚氯乙烯球晶表面的XPS研究

聚合物薄膜在微电子领域中的应用日益增加.聚ε-己内酯/聚氯乙烯（PCL/PVC）是研究得最广泛的聚合物共混薄膜之一.PCL与PVC以一定比例混合时,可以形成环带球晶；同时,体系分为结晶PCL相及PCL/PVC非晶混溶相.用XPS和成象XPS分析技术,对PCL/PVC膜的表面化学组成和元素分布情况进行了研究.观察到PCL在薄膜表面富集.此外,成象XPS表明,PVC在球晶边界处富集,且球晶边界宽度约15 μm.     

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。     

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.     

聚苯乙烯，聚甲基丙烯酸甲酯对聚氯乙烯／氯化聚乙烯共混体流变性的影响

聚苯乙烯，聚甲基丙烯酸甲酯对聚氯乙烯／氯化聚乙烯共混体流变性的影响杨文君，吴其晔，杜华（青岛化工学院高分子材料系，青岛，２６６０４２）王建民，李应华，张宝善（齐鲁石化研究院，淄博，２５５４３４）关键词塑料改性，流变性，聚氯乙烯，氯化聚乙烯，刚性粒子我...     

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。     

PVC/EVA-g-VC共混物的形态与加工条件和性能的关系

PVC/EVA(-14)及 PVC/EVA(-14)-g-VC的等速升温Brabender塑化曲线上有两个扭矩峰,分别标志着EVA和PVC的塑化,对应着共混形态经历的三个变化:(1)EVA塑化——PVC粉粒破碎;(2)EVA呈连续相——PVC集结粒子解体;(3)EVA呈分散相——PVC初级粒子熔化。聚合投料比(VC/EVA)越小,EVA-g-VC的塑化温度和熔体粘性越高,两个扭矩峰靠得越近。实验结果表明,EVA-g-VC与EVA相比,不仅与PVC有更好的相容性,而且有较好的均匀可混性。冲击强度的测定结果表明:EVA连续网——PVC初级粒子结构具有较高的冲击强度。VC/EVA较小时所得EVA-g-VC改性的PVC可在较宽的加工温度范围保持EVA连续网结构和较高的冲击强度。     

STUDY ON THE MORPHOLOGY OF POLYVINYL CHLORIDE/POLYSTYRENE BLENDS BY ELECTRON MICROPROBE ANALYSIS*

The morphology of polyvinyl chloride/polystyrene (PVC/PS) blend samples with different mass ratios, preparedby means of solution casting and melt mixing, have been successfully examined by electron microprobe analysis (EMP). Thisexperiment was performed in a scanning electron microscope attached to an energy dispersive X-ray analyzer. Differentialscanning calorimetry was also used to investigate the phase separation of the blends. The results show that PVC and PS areincompatible and the blends have sea-islands phase structures. Blends prepared via melt mixing have finer phase-dispersionthan those prepared via solution casting.     

Preparation and characterization of thermoplastic elastomer of poly(vinyl chloride) and chlorinated waste rubber

In order to develop applications for the abundant waste rubber powder, chlorinated waste rubber (Cl-WR) was prepared by a water based chlorination method using chlorine as chlorinating agent. In this paper, Cl-WR was used as an elastic filler and blended with poly(vinyl chloride) (PVC) matrix to develop a new thermoplastic elastomer PVC/Cl-WR. The mechanical properties, hydrophilicity, swelling resistance, morphology and thermal properties of PVC/Cl-WR were characterized and compared with those of PVC/waste rubber powder (PVC/WR) blends. The results indicated that the mechanical properties, hydrophilicity, swelling resistance and thermal properties of the PVC/Cl-WR blends showed noticeable improvements over PVC/WR blends due to the improved polarity of Cl-WR. Also, the excellent miscibility and compatibility of Cl-WR with PVC was demonstrated by scanning electron microscope (SEM) images of the resulting blends.     

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.     

FTIR studies of polar interactions in polymer blends

Specific interactions in binary blends of poly(vinyl chloride) (PVC) with ethylene–vinyl acetate copolymers (EVA) and ethylene-methyl acrylate copolymers (EMA) were investigated by observation of band shifts of the carbonyl absorption using ATR-FTIR spectroscopy at variable temperature. Blends of PVC with EVA and EMA could be prepared as heterogeneous, homogeneous or metastable homogeneous mixtures, depending on the copolymer composition. The miscible systems as well as the heterogeneous ones showed only very small or no band shifts. The metastable blends exhibited shifts of several wave numbers to lower values, which vanished at higher temperatures as the blends demixed. Strong interactions in the metastable blends could be related to good impact properties of the corresponding two-phase systems.