EVA-g-VC的结构和动态粘弹性

本文研究了聚乙烯-醋酸乙烯酯(EVA,VAc:14％)与氯乙烯(VC)接枝共聚物(EVA-g-VC)的相结构和分子结构。接枝物EVA-g-VC由游离EVA、均聚PVC和EVA-VC接枝高分子三者组成,EVA呈连续相,PVC呈分散微粒。EVA-g-VC中EVA的含量越高,PVC粒子体积越小。实验结果表明,接枝物中“凝胶”的EVA玻璃化温度,随投料比(VC/EVA)的减小而升高;另外随VC/EVA减小,凝胶中PVC的含量和PVC的分子量也减小。这些结果说明,VC/EVA较小时得到的接枝物中,EVA上VC接枝点的数目较多,而PVC接枝链的长度较短。EVA-VC是不相容两相——EVA和PVC的“粘着剂”,其作用表现在:VC/EVA越小,接枝物中EVA和PVC的玻璃化温度越靠近。     

氯乙烯在高聚物中的溶解度

本文进行了氯乙烯在氯相/高聚物 (PVC,EVA,EVA-g-VC) 间相平衡的研究。实验数据用三种数学模型作了处理:Flory-Huggins 经典模型、Prigogine-Flory 自由容积模型和本文作者提出的线性模型。氯乙烯在高聚物中的溶解度按三种模型的计算值与实验结果都符合得很好。而且,结果表明,线性模型具有精确易用的优点,Prigogine-Flory 模型完全适用于 VC/PVC体系,VC在EVA-g-VC接枝共聚树脂中的溶解度服从加和性规律。     

ASA对PVC塑化和冲击性能影响

以聚丙烯酸丁酯（PBA）为核,苯乙烯（St）、丙烯腈（AN）的共聚物为壳,采用种子乳液聚合法制备了一系列丙烯酸丁酯-苯乙烯-丙烯腈（ASA）核壳接枝共聚物。考察了ASA的用量、ASA中核层质量分数和ASA壳层中AN的质量分数对聚氯乙烯（PVC）塑化和冲击性能的影响。结果表明：随着ASA用量的增加,PVC熔融时间缩短,最大扭矩和平衡扭矩增大;断面的扫描电镜图证实了PVC脆-韧转变过程;随着ASA核层质量分数的增加,熔融时间略有缩短,扭矩略有增加,PVC的冲击强度增加幅度不大;随着ASA壳层中丙烯腈的质量分数增加,熔融时间变化不大,但扭矩逐渐增加;当丙烯腈质量分数超过0.40时,PVC的冲击强度开始下降。     

PVC/MBS/纳米 BaSO4 复合材料的制备及其性能

采用熔融共混法制备聚氯乙烯(PVC)/甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)/纳米重晶石(nano-BaSO4)三元复合材料,考察其力学性能和热稳定性能,并用扫描电镜观察冲击断面的形态.结果表明:MBS 与 nano-BaSO4 可协同增韧 PVC;当 MBS、nano-BaSO4 的含量分别为 10%、1%时,材料的韧性和刚性可同时得以改善,其冲击断面表现出典型的韧性断裂特征;热重分析显示添加 1%nano-BaSO4 可显著提高 PVC/MBS 的热稳定性能,其第一降解阶段的初始分解温度和最快分解温度分别提高了 10℃和14℃.     

聚氯乙烯/α-甲基苯乙烯-丙烯腈共混体系的相容性和性能研究

选用腈基含量为30%的α-甲基苯乙烯-丙烯腈(α-MSAN)作为聚氯乙烯(PVC)的耐热改性剂,通过熔融共混制备了PVC/α-MSAN共混材料.通过SEM、DSC、DMA及透光率测试等手段系统研究了α-MSAN的含量对PVC/α-MSAN共混体系相容性的影响,发现在高达60%(wt)的α-MSAN的含量范围内它们具有良好的相容性,并从分子结构上解释了其相容性良好的原因;随α-MSAN含量增加,共混体系的维卡软化温度(VST)和拉伸强度上升,冲击强度下降;α-MSAN的引入会导致共混体系及PVC静态热稳定时间下降,共混体系的颜色加深.同时分析了α-MSAN对共混体系耐热性能、热稳定性能和力学性能产生影响的机理.     

力化学降解对聚氯乙烯加工流变行为的影响

采用Brabender塑化仪和毛细管流变仪研究了经力化学降解制得的聚氯乙烯(PVC)的加工流变行为。结果表明,降解的PVC塑化时间比未降解的PVC明显缩短,塑化速度和熔化效率也明显加快,熔体粘度及玻璃比温度降低。     

部分水解聚甲基丙烯酸甲酯/氢氧化钙复合物对硬质聚氯乙烯热稳定性与透明性及塑化行为的影响

采用溶液沉淀法制备了部分水解的聚甲基丙烯酸甲酯(h-PMMA)/氢氧化钙(Ca(OH)2)复合物.采用X-射线衍射(XRD)、红外光谱(FTIR)、等离子体发射光谱和差示扫描量热表征了h-PMMA/Ca(OH)2复合物的组成与结构;采用刚果红测试、动态热稳定测试和热失重分析(TGA)研究了复合物对聚氯乙烯(PVC)的热稳定效果;通过紫外-可见(UV-Vis)光谱、扫描电镜(SEM)照片和熔融塑化曲线研究了复合物对PVC透明性和塑化行为的影响.结果表明,在Ca(OH)2晶体生长过程中,h-PMMA通过—COO-/Ca2+离子配位作用吸附于Ca(OH)2表面,不仅限制了Ca(OH)2粒子尺寸,且有助于Ca(OH)2在PVC中均匀分散.所得h-PMMA/Ca(OH)2复合物在显著提高PVC热稳定性和塑化能力的同时,还使PVC保持透明性.     

聚氯乙烯/纳米水滑石复合材料的形态与力学性能

对由原位悬浮聚合制备的聚氯乙烯(PVC)纳米水滑石复合树脂加工得到的纳米复合材料的形态和力学性能进行了研究,并与直接熔融加工得到的PVC纳米水滑石复合材料进行比较.发现由前一方法得到的PVC纳米水滑石复合材料中纳米水滑石的分散性明显优于由后一方法得到的PVC纳米水滑石复合材料,水滑石以初级粒子形式存在,分散良好,无明显团聚体;与之对应,由前一方法得到的PVC纳米水滑石复合材料的力学性能也明显优于由后一方法得到的PVC纳米水滑石复合材料,当纳米水滑石含量小于5wt%时,复合材料的杨氏摸量、拉伸强度和缺口冲击强度均随水滑石含量增加而增大;纳米水滑石的引入可显著提高复合树脂的热稳定性;PVC纳米水滑石复合材料的储能和损耗模量略大于纯PVC材料,而损耗因子和玻璃化温度变化不大.     

无水AlCl_3催化PVC/PS反应性增容的研究

以无水AlCl3为催化剂,通过聚氯乙烯(PVC)与聚苯乙烯(PS)之间Friedel-Crafts反应,实现了PVC/PS共混体系的反应性增容,使PVC与PS熔融共混温度由160℃降为140℃;通过预碾磨和加入苯乙烯(St)的方法,提高材料韧性,制备了综合力学性能良好的PVC/PS合金材料.应用FTIR、DSC、SEM和力学性能测试等手段表征了合金材料的结构与性能.结果表明,FTIR出现了1943和838 cm-12个苯环对位被取代的特征吸收峰;DSC在89℃出现了玻璃化转变;SEM证明PVC/PS两相界面粘接性随AlCl3、St的加入越来越好.在PS、AlCl3和St的质量分数分别为6%,0.6%和9%时,实现了对PVC的增强增韧.合金拉伸强度达到60.54MPa,比PVC的49.35 MPa提高了22.7%;缺口冲击强度达到5.3 kJ/m2,比PVC的3.9 kJ/m2提高了35.9%.     

PVC/ABS共混塑料结构与性能的研究

本文利用透射电镜观察PVC/ABS共混塑料的结构,结合其流变性能,机械性能,探讨结构与性能之间的关系。结果表明,PVC/ABS共混望料的热性能,抗冲击强度介于纯PVC和ABS之间,而缺口冲击强度则优于PVC和ABS,且当ABS含量为30％时有个最大值,这是由于PVC/ABS共混塑料的微观结构造成的。PVC/ABS共混塑料随着ABS含量的减少,“橡胶”粒子变小,当ABS含量为30％时,二组分相容性最好。     

含氯聚合物和乙烯-醋酸乙烯酯共聚物共混体系的红外光谱研究

关于氯化聚乙烯(CPE)或聚氯乙烯(PVC)与乙烯—醋酸乙烯酯共聚物(EVA)共混体系相容性的研究,已有不少报道,其中Coleman等人运用FTIR方法研究了含VA45％的EVA与CPE、PVC的共混体系,测定了该体系的低临界共溶温度(LCST)。一般认为,如果VA含量更低,由于EVA本身的结晶,共混体系将变得难以     

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.     

反相气相色谱法研究聚合物共混物的相溶性

 用反相气相色谱法测定了聚氯乙烯(PVC)／ 乙烯-醋酸乙烯共聚物(EVA)共混体系中分子间表观热力学相互作用参数χ′23,并以χ′23 为判定依据,研究了共混物的相溶性。 初步探讨了共混物的组成、聚合物分子 链结 构、温度与χ′23的关系以及探针分子性质 对χ′23参数的影响。结果表明：χ[ HT6〗′23值能够准确有效地判定PVC与EVA共混物的 相溶性,醋酸乙烯质量分数低的EVA与PVC的共混物是热力学不相溶的;而醋酸乙烯质量 分数中等的EVA与PVC的共混物则具有部分相溶性。结果与其它方法得到的结论是一致的 。     

Effect of the liquid–liquid phase separation on the crystallization behavior and mechanical properties of poly(ethylene‐ran‐vinyl acetate) and paraffin wax blend

The effect of liquid–liquid phase‐separation (LLPS) on the crystallization behavior and mechanical properties of poly(ethylene‐ran‐vinyl acetate) (EVA) with various amounts of vinyl acetate and paraffin wax blend was investigated. The blend of EVA‐H (9.5% vinyl acetate) and the wax became homogeneous at temperatures greater than its upper critical solution temperature (UCST) (98°C), and an LLPS was observed between UCST and the melting point of 88°C for EVA‐H in the blend. The existence of the LLPS is attributed to the relatively large amount of the hydrophilic component of vinyl acetate in EVA, although the molecular weight of the wax was just 560. However, LLPS did not occur for the EVA/wax blend when the content of vinyl acetate in EVA was less than 3%. This behavior was explained by using the Flory–Huggins lattice model with an effective interaction parameter. The degree of crystallinity of EVA‐H in the EVA‐H/wax blend, judged from a melting endothermic peak in differential scanning calorimeter (DSC) thermograms obtained during heating runs, decreased with increasing duration time in the LLPS region. The flexural modulus of the EVA/wax blend became maximum at certain blend composition (about 30 ∼ 40 wt % EVA depending upon the amount of vinyl acetate). This behavior can be explained by the fact that this blend composition has the largest relative degree of crystallinity of EVA measured by DSC and wide‐angle X‐ray scattering method. We found that the flexural modulus of the binder itself is directly related to that of a feedstock consisting of larger amounts of metal powder and the binder, which can help someone to develop a suitable binder system for a powder injection molding process. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1991–2005, 1999     

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。     

Effect of the liquid–liquid phase separation on the crystallization behavior of a poly(ethylene‐ran‐vinyl acetate) and paraffin wax blend

The effect of liquid–liquid phase separation (LLPS) on the crystallization behavior of poly(ethylene‐ran‐vinyl acetate) with a vinyl acetate content of 9.5 wt % (EVA‐H) in the critical composition of a 35/65 (wt/wt) EVA‐H/paraffin wax blend was investigated by small‐angle light and X‐ray scattering methods and rheometry. This blend exhibited an upper critical solution temperature (UCST) of 98°C, and an LLPS was observed between the UCST and the melting point of 88°C for the EVA‐H in the blend. As the duration time in the LLPS region increased before crystallization at 65°C, both the spherulite size and the crystallization rate of the EVA‐H increased, but the degree of the lamellar ordering in the spherulite and the degree of crystallinity of the EVA‐H in the blend decreased. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 707–715, 2000     

乙烯醋酸乙烯酯/聚氯乙烯共混体系相容性、相逆转及其物理力学性能研究

<正> 硬质聚氯乙烯(PVC)由于韧性较差通常要用改性剂改善其抗冲击性能。但要使改性剂能有效起到作用,必须考虑它与PVC之间的相容性及其配比等对共混物性能的影响。本工作从动态力学及其他物理力学性能,研究了含48%醋酸乙烯(VAc)的乙烯醋酸乙烯酯共聚物(EVA)与PVC共混时组分之间的相容性及其配比对体系相逆转及其物理力学性能的影响。 样品:PVC采用北京化工二厂生产的SX-4型粉料。EVA粒料中的VAc重量含量为48%。将这两种料按不同的比例,加上助剂(二盐基亚磷酸铅、三盐基硫酸铅、硬     

Electrically conductive,melt‐processed ternary blends of polyaniline/dodecylbenzene sulfonic acid,ethylene/vinyl acetate,and low‐density polyethylene

Although polyaniline (PANI) has high conductivity and relatively good environmental and thermal stability and is easily synthesized, the intractability of this intrinsically conducting polymer with a melting procedure prevents extensive applications. This work was designed to process PANI with a melting blend method with current thermoplastic polymers. PANI in an emeraldine base form was plasticized and doped with dodecylbenzene sulfonic acid (DBSA) to prepare a conductive complex (PANI–DBSA). PANI–DBSA, low‐density polyethylene (LDPE), and an ethylene/vinyl acetate copolymer (EVA) were blended in a twin‐rotor mixer. The blending procedure was monitored, including the changes in the temperature, torque moment, and work. As expected, the conductivity of ternary PANI–DBSA/LDPE/EVA was higher by one order of magnitude than that of binary PANI–DBSA/LDPE, and this was attributed to the PANI–DBSA phase being preferentially located in the EVA phase. An investigation of the morphology of the polymer blends with high‐resolution optical microscopy indicated that PANI–DBSA formed a conducting network at a high concentration of PANI–DBSA. The thermal and crystalline properties of the polymer blends were measured with differential scanning calorimetry. The mechanical properties were also measured. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3750–3758, 2004