POE-g-PMAH反应性增容PA1010/PP共混物的性能研究

乙烯-辛烯共聚物-g-聚马来酸酐(POE-g-PMAH)作为反应性增容剂,采用熔体共混的方法制备了PA1010/PP共混物,通过扫描电镜(SEM)、力学性能、傅立叶变换红外光谱(FTIR)和示差扫描量热(DSC)测试,研究了POE-g-PMAH对PA1010/PP共混物的增容作用.结果表明,POE-g-PMAH的加入可以减小共混物的相区尺寸,当PA1010/PP/POE-g-PMAH=70/30/15时,分散相尺寸小而均匀;FTIR结果表明接枝在POE上的马来酸酐基团和PA1010在熔融共混期间发生了化学反应;DSC研究结果表明共混体系中PA1010和PP的结晶温度和结晶度随POE-g-PMAH的加入而降低,表明POE-g-PMAH的增容作用对PA1010和PP的结晶有抑制作用.力学性能测试结果表明随着POE-g-PMAH的增加,共混物的冲击强度逐渐增加,当POE-g-PMAH含量增加到15%时,干态冲击强度达到21.13 kJ/m2,是不加增容剂的3.1倍,而拉伸和弯曲强度可以保持较高水平.POE-g-PMAH的增容机理在于其支链中的马来酸酐能与PA1010中的胺基(NH2—)发生化学反应,而主链POE与PP有较好的亲和性,从而降低界面张力,减少相区尺寸,大幅度提高力学性能.     

PP-g-(MAH/St)和PP-g-MAH对聚丙烯/木粉复合材料性能的影响

在转矩流变仪中用熔融接枝法制备马来酸酐(MAH)和苯乙烯(St)接枝聚丙烯（PP）-PP-g-(MAH/St)和PP-g-MAH,将其作为聚丙烯/木粉复合材料的相容剂。 FTIR证实MAH和St单体与PP发生接枝反应。 用SEM和DSC等手段考察两种相容剂对PP/木粉复合材料微观形貌和结晶性能的影响,探索了各种PP/木粉复合材料加工和力学性能不同的内在原因。 SEM显示,PP-g-(MAH/St)改性木粉比PP-g-MAH改性木粉在PP基体中分散性更佳,木粉与PP的界面更加模糊,相容性进一步改善。 DSC结果表明,PP-g-(MAH/St)改性体系可增强木粉对PP的异相成核作用,提高结晶温度和结晶度。 复合材料的加工和力学性能测试结果表明,PP-g-(MAH/St)改性效果明显优于PP-g-MAH。 复合材料的熔体质量流动速率随相容剂用量的增加而逐步下降,PP-g-(MAH/St)改性体系拉伸强度和弯曲强度却逐步上升,并在相容剂用量为4.8 g/100 g PP时达到极值。 此时其拉伸强度达40.62 MPa,分别是未改性体系和PP-g-MAH改性体系的1.29和1.17倍;其弯曲强度达45.72 MPa,分别是未改性体系和PP-g-MAH改性体系的1.23和1.59倍;而无缺口冲击强度却在相容剂用量为3.6 g/100 g PP时达到极值13.35 kJ/m2,分别是未改性体系和PP-g-MAH改性体系的1.62倍和1.42倍。     

双路易斯酸催化原位增容乙烯辛烯共聚物/苯乙烯共混物的研究

采用新型双路易斯酸, 三甲基氯硅烷和三氯化铟,为催化剂引发傅氏烷基化反应,实现了乙烯辛烯共聚物（POE）和聚苯乙烯（PS）共混物的原位增容。红外光谱验证了接枝物的存在。用扫描电镜观察了反应共混体系和简单物理共混物的形态, 前者分散相的尺寸小于1 μm, 后者分散相的尺寸则较大, 一般为3～4 μm。原位生成的接枝物起到相容剂的作用,增容后的样品的力学性能得到较明显的提升。如：当POE /PS 为40/60 (wt%) 时, 与相同组成的物理共混的POE/PS 相比, 其悬臂梁冲击强度由1.9 kJ/m2 增加到9.7 kJ/m2, 断裂伸长率由3.4%提高到46.3%。增容后共混物的流变性能与物理共混物相比也发生了显著的变化。     

PTW对PA1010/PP共混物的增容作用

为了增加聚酰胺1010/聚丙烯(PA1010/PP)共混物的相容性,提高共混物的力学性能,采用一种新型的反应型增容剂乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物(PTW)进行增容,通过扫描电镜(SEM)、力学性能、傅里叶变换红外光谱(FTIR)和差示扫描量热(DSC)测试,研究了PTW对PA1010/PP共混物的增容作用.结果表明,随着PTW的加入,共混物的相区尺寸明显变小,当PA1010/PP/PTW质量比为70∶30∶7时,分散相尺寸细小而均匀,表明PTW有较好的增容作用.FTIR结果表明,PTW上的环氧基团和PA1010在熔融共混中发生了化学反应.DSC研究结果表明,PA1010的结晶温度随PTW的加入而降低,说明PTW对PA1010结晶有抑制作用.另外,PTW的加入使PP的结晶温度下降,当PTW质量分数为5%时出现2个结晶峰,即出现异相成核结晶和均相成核结晶,PP均相成核结晶的出现从另一个方面说明,在PA1010基体中分散相PP尺寸非常细小.当PTW质量分数为7%时共混物的力学性能最佳,干态冲击强度达到13.93kJ/m2,是未加增容剂时的2倍,拉伸和弯曲性能基本不变.PTW的增容机理在于其分子链中的甲基丙烯酸缩水甘油酯能与PA1010发生化学反应,而乙烯链段与PP有较好的亲和性,从而降低界面张力,减少相区尺寸,大幅度提高力学性能.     

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.     

Versify-g-(MAH-co-St)对改善PA6/Versify共混物增韧和均衡其力学性能的影响

使用挤出机对乙丙共聚物Versify2300(乙烯含量12wt%)(V-2300)进行马来酸酐(MAH)和苯乙烯(St)多单体熔融接枝得到接枝物Versify-g-(MAH-co-St)(g-V-2300).通过SEM、FTIR和力学性能测试,研究了g-V-2300对PA6/(V-2300+g-V-2300)(70/30)共混物形态和性能的影响.研究结果表明,随着g-V-2300含量的提高,V-2300分散相粒径不断减小且分散均匀.当g-V-2300比例为25wt%时,分散相尺寸只有0.27μm,此时共混物的izod冲击强度达到324.54J/m,为PA6/(V-2300+g-V-2300)(70/(30+0))共混物的16倍.g-V-2300的加入,显著改善了PA6/(V-2300+g-V-2300)(70/30)共混物的冲击强度,其伸长率,拉伸强度和抗弯强度也得到提高,从而得到具有均衡力学性能的增韧尼龙6合金.     

F-C烷基化反应原位增容PS/POE共混物中降解的抑制和增容效果的优化

在聚苯乙烯(PS)/聚烯烃弹性体(POE)/AlCl3共混物中引入苯乙烯(St)单体,增加了共混体系中的不饱和结构,AlCl3催化剂与St反应生成大量的初始碳正离子,这些初始碳正离子进攻POE链生成更多的大碳正离子,进而形成更多的PS-graft-POE共聚物,提高了接枝效率.进而,采用"两次挤出"技术,即先原位增容制成接枝母料,然后接枝母料再与PS和POE二次挤出,可以在一定程度上缓解组份的降解,使共混物的力学性能得到进一步的改善.     

PBT/POE-g-MAH/PP共混体系的相态结构与性能

采用马来酸酐接枝乙烯-辛烯共聚物弹性体(POE-g-MAH)与聚丙烯(PP)在双螺杆挤出机上进行熔融共混,制备了3种新型增韧改性剂.研究了增韧改性剂的种类及其用量对共混物的力学性能、相形态结构、熔融与结晶行为的影响.力学性能测试表明,POE-g-MAH与适量PP并用具有显著的协同增韧作用,当POE-g-MAH与PP的配比为70/30时,所得增韧改性剂(POEg2)具有最佳的增韧效果.当POEg2含量达到15%时,共混物的缺口冲击强度(Is)从纯PBT的7.5 kJ/m2提高到51.2 kJ/m2,与15%的纯POE-g-MAH弹性体增韧PBT具有相近的缺口冲击强度值.同时,共混物的拉伸强度(σb)损失最小.采用AFM和SEM观察发现,新型增韧改性剂作为分散相具有软壳-硬核结构.DSC测试表明,随增韧改性剂中PP含量增加到一定值时,壳-核结构中软壳层出现不完整现象,导致界面作用力减小,共混物的Is和σb都出现明显下降.     

聚丁二酸丁二酯/纳米高岭土共混体系结晶及力学性能研究

用熔融共混法制备聚丁二酸丁二酯(PBS)/纳米高岭土(nano kaolin)复合降解材料,利用FTIR、DSC、万能拉力机和SEM对其微观结构、结晶、力学性能及分散性进行研究.FTIR光谱分析结果表明,改性剂与nano kaolin发生了化学键合作用;DSC结果表明,在PBS中加入nano kaolin,提高了结晶起...     

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     

微波辐照实现PVC-PS之间的Friedel-Crafts接枝反应

在四氢呋喃、环己酮等溶液中实现了聚氯乙烯(PVC)与聚苯乙烯(PS)的Friedel-Crafts接枝反应,考察了加热方式、反应温度、催化剂种类、催化剂用量对接枝反应的影响,通过FTIR表征了PVC-g-PS接枝物的结构,探讨了反应的机理和特点.研究发现,油浴加热和微波辐照都能使PVC和PS发生接枝反应,但微波辐照效果更好,油浴加热,接枝率仅0.27%,而微波辐照接枝率高达23%;油浴加热时产物少且多为间位,微波辐照时产物多且多为对位和邻位.无水AlCl3、无水FeCl3、无水SnCl4皆对PVC与PS之间的Friedel-Crafts反应具有催化活性,其中无水AlCl3的催化活性最高,其最佳用量为质量分数3%,此时,接枝率达到29%.当无水AlCl3过高时,PVC降解,产生双键,接枝率下降.表明微波辐照是实现PVC与PS之间Friedel-Crafts接枝反应的有效途径.     

The influence of core-shell structured modifiers on the toughness of poly (vinyl chloride)

The core-shell structured grafted copolymer particles of polybutadiene grafted polymethyl methacrylate (PB-g-PMMA, MB) were prepared by emulsion polymerization. The MB particles were used to modify poly (vinyl chloride) (PVC) by melt blending. The mechanical properties of the PVC blends were investigated. The micro-morphology of the PVC blends was observed by scanning electron microscopy (SEM). The results indicated that the samples with the best impact strength could be obtained when the core-shell weight ratio of PB to PMMA is lower than 93:7, the mechanical properties correlated well with SEM morphologies, the addition of modifier with the ratio core to shell of 93:7 could reduce the domain size of the dispersed phase. Furthermore, the compatibility and properties of the blends were greatly enhanced and improved. The modifier particles could be well dispersed in the PVC matrix.     

铌酸银可见光催化降解聚氯乙烯薄膜

采用涂层法在玻璃基底上分别制备了纯聚氯乙烯(PVC)薄膜和添加水热法制备的钙钛矿型铌酸银(AgNbO₃)光催化剂的复合薄膜(PVC-wAgNbO₃, 其中w为AgNbO₃的质量分数), 在500 W氙灯照射120 min条件下进行了薄膜的光催化降解实验. 利用X射线衍射仪(XRD)、 扫描电子显微镜(SEM)和傅里叶变换红外光谱仪(FTIR)等对光照前后薄膜的形貌及光催化降解过程进行了表征. 结果表明, 在光催化降解过程中纯PVC薄膜失重率为4.09%, 而PVC-3%AgNbO₃, PVC-6%AgNbO₃, PVC-9%AgNbO₃和PVC-15%AgNbO₃复合薄膜分别失重20.36%, 23.52%, 27.62%和33.83%. AgNbO₃光催化剂加速了PVC薄膜的降解, 且随着AgNbO₃光催化剂添加量的增加, PVC薄膜的光催化降解速率不断增大.     

基于热重红外联用分析的PE、PS、PVC热解机理研究

利用TGA-FTIR联用技术考察了PE、PS、PVC三种典型塑料的热解特性。结果表明,热稳定性从弱到强依次为PVC、PS、PE。PE热解反应过程为典型的一段式反应,红外光谱分析结果表明,PE热解过程为无规则断链形式,生成产物成分复杂,且随热解过程而改变,开始以饱和烃基团为主,中后期以烯烃基团为主,同时有少量炔烃;PS热解过程同样为一段式反应,红外光谱显示主要热解产物为苯乙烯单体,说明热解过程主要是苯乙烯的解聚过程;PVC热解过程较为复杂,主要分为脱氯阶段和共轭多烯重构阶段,红外光谱结果表明,产物中有芳香族化合物。脱氯过程和共轭多烯重构、环化过程在时间和空间上有重合,给二噁英类污染物的生成制造了可能。     

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.     

Nanotubes as polymer composite reinforcing additive materials – A comparative study

Nitrogen-doped bamboo-shaped carbon nanotubes (N-BCNTs) and their non-doped conventional counterparts, multiwalled carbon nanotubes (MWCNTs) were compared as polymer reinforcing additives in polyvinyl chloride (PVC) matrix. The nanotubes were synthetized by catalytic chemical vapor deposition (CCVD) method. The purity of both nanotubes was measured by thermogravimetric analysis (TGA) and found to be >91%. Further analysis on the morphology and size of the carbon nanotubes (CNTs) were performed by transmission electron microscopy (TEM). The PVC powder was impregnated with CNTs in ethanol by using tip ultrasonicator. The dispersion media was evaporated, and the CNT/PVC powder was used to produce polymer fibers. The orientation of carbon nanotubes in the PVC matrix was characterized by scanning electron microscopy (SEM), and the presence of nanotubes were confirmed in case of all PVC samples. It can be observed on the SEM images that the nanotubes are fully covered with PVC. The tensile strength of the nanotube containing samples was tested and the N-BCNT/PVC composite was found to be better in this sense, thanks to the extraordinary structure of the nanotube. In case of the N-BCNT/PVC composite the measured young modulus was 39.7% higher, while the elongation at brake decreased by 33.6% compare to the MWCNT/PVC composite. These significant differences in the mechanical properties of the composites can be explained with the stronger interaction between N-BCNTs and PVC.     

A study of three-layered latex interpenetrating polymer networks used as processing modifiers and impact modifiers of thermo-plastic resins

In this paper, the latex interpenetrating polymer network poly(n-butyl acrylate) polystyrene/poly(methyl methacrylate) (PBA/PS/PMMA, or PBSM) was synthesized by microagglomeration and three-stage emulsion polymerization. The initial poly(n-butyl acrylate) latex particle was agglomerated by methacrylic acid residue containing the polymer latex and then encapsulated by PS and PMMA. The polyblend of poly(vinyl chloride) (PVC) and PBSM (PVC/PBSM) was prepared by blending PVC and PBSM. The morphology and properties of the polyblend have been studied. Experimental results have shown that the processability and impact-resistance of PVC can be enhanced considerably by means of blending 6–20 per hundred resin (phr) PBSM. The three-layered latex interpenetrating polymer network is a promising modifier for rigid PVC (RPVC) manufactures.     

Nitroxide mediated living radical polymerization of styrene onto poly (vinyl chloride)

Nitroxide‐mediated ‘living’ free radical polymerisation (LREP) was employed for the first time to prepare graft copolymer by having arylated poly (vinyl chloride) (PVC‐Ph) as a backbone and polystyrene (PS) as branches. The graft copolymerization of styrene was initiated by arylated PVC carrying 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) groups as a macroinitiator. Thus, the arylated PVC was prepared in the mild conditions and these reaction conditions could overcome the problem of gelation and crosslinking in polymers. Then, 1‐hydroxy TEMPO was synthesized by the reduction of TEMPO with sodium ascorbate. This functional nitroxyl compound was coupled with brominated arylated PVC (PVC‐Ph‐Br). The resulting macro‐initiator (PVC‐Ph‐TEMPO) for ‘living’ free radical polymerization was then heated in the presence of styrene to form graft copolymer. DSC, GPC, ¹HNMR, and FT‐IR spectroscopy were employed to investigate the structure of the polymers. Copyright © 2007 John Wiley & Sons, Ltd.     

PS/PVC互贯大孔吸附树脂对脲酸的吸附研究

大孔球状PVC经苯乙烯的自由基互穿聚合反应改性得PS PVC大孔互贯树脂 ,再与有机胺反应制得了PS PVC互贯含氮大孔吸附树脂 .研究表明 ,所得吸附树脂对脲酸的吸附率可达 5 0 %以上 ,在清除体液中过量脲酸方面具有应用潜力 .同时对吸附树脂含氮量与吸附脲酸性能的关系以及其它因素的影响也进行了探讨