ABS的MAH/St多单体熔融接枝及其对PA6/ABS共混体系相形态和力学性能的影响

通过多单体熔融接枝的方法制备出了具有较高接枝率的ABS接枝物 (ABS g (MAH co St) ) ,并对其接枝机理进行了初步探讨 .研究表明 ,MAH、St接枝ABS时 ,反应主要发生在ABS中聚丁二烯的双键部位 .同时 ,当MAH与St的用量比约为 1:1时接枝率达到最高 .ABS g (MAH co St)作为尼龙 6 (PA6 ) ABS共混体系相容剂起到了良好的增容效果 .实验证明 ,相容剂使用前后 ,共混物的相区尺寸由几十 μm减小到 1μm以下 ,且分布更加均匀 ;共混物的拉伸强度和冲击强度等力学性能也同时得到均衡改善 .     

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.     

交联PBA／SAN核—壳乳液接枝共聚研究

ABS是一种性能优异的树脂,但由于橡胶相含有双键而耐候耐热性差,本文试图以交联的聚丙烯酸丁酯为核,合成PBA/SAN核-壳乳液接枝共聚物。考察了核-壳乳液接枝共聚物的定量组成和微观结构。结果表明:接枝物组成近似于其乳液恒比组成;接枝率、接枝效率、分子量和接枝层,壳层厚度随聚合过程参数的改变而呈规律性变化,损耗正切峰表明在种子聚合物相中存在SAN聚合物的微相区。     

水辅助注塑PP/SAN共混物制品中横晶形成机理的研究

采用水辅助注塑(WAIM)设备,在不同的注水压力和熔体温度下制备了4种质量比(98/2,96/4,94/6和92/8)的聚丙烯/丙烯腈-苯乙烯共聚物(PP/SAN)共混物制品.采用偏光显微镜(POM)和扫描电子显微镜(SEM),研究了WAIM PP/SAN共混物制品的结晶形态和相形态.研究发现,高压水的穿透作用所引起的强剪切和快速冷却可诱导SAN在PP基体中原位成纤,并诱导PP在SAN纤维表面形成大量的晶核而最终形成横晶.SAN含量为4 wt%时,所形成横晶的含量随水压的提高而增加,随温度的降低而大幅增加.当SAN含量较低(2 wt%)时,制品中没有横晶形成.     

接枝共聚物EPR-g-PS作PS/EPDM共混体系增容剂的探讨

使用了由大分子单体共聚合制备的以乙丙橡胶(EPR)为主干、聚苯乙烯(PS)为支链的接枝共聚物EPR-g-PS作为PS/EPDM共混体系的增容剂。实验结果表明,共混体系的组成、增容剂加入量以及增容剂分子结构对共混体系冲击强度有很大影响。将这些因素与相差显微镜及扫描电镜研究所揭示的共混物形态的变化相联系,对此类接校共聚物作为不相容体系增容剂的机理作了探讨。     

SMA、OMMT对PA6/ABS共混物聚集态结构及性能影响的研究

采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)等手段研究了苯乙烯-马来酸酐共聚物(SMA)、有机蒙脱土(OMMT)对尼龙6(PA6)/丙烯腈-丁二烯-苯乙烯(ABS)共混物体系聚集态结构及性能的影响.结果表明,SMA与OMMT的加入均可提高PA6/ABS共混物体系的强度及模量,但加入OMMT后共混物的韧性有所下降,而PA6/ABS/SMA共混物的韧性随SMA含量的增加呈上升趋势.SMA、OMMT对PA6/ABS共混体系都有细化ABS分散相的作用,随SMA加入量的增加,ABS分散相尺寸逐渐减小,分布趋于均匀;当OMMT加入量在4 phr以内时,对ABS分散相粒径影响不大,超过4 phr后,随着OMMT含量的增加,ABS分散相的尺寸逐渐减小.XRD与TEM的分析结果表明,对PA6/OMMT(100/5)共混物,OMMT主要以剥离形态分布,同时也存在少量OMMT聚集体;PA6/ABS/OMMT共混物中OMMT则基本以剥离形态选择分布在PA6基体相中.     

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。     

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。     

SiO2粒子对PMMA/SAN共混体系相分离行为的影响

采用小角激光光散射(SALLS)并结合动态流变学方法,考察了气相法二氧化硅(SiO2)粒子的加入对聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物(PMMA/SAN)共混体系相行为的影响,得到了添加SiO2粒子前后的相图,发现SiO2粒子对基体相行为的影响与基体的组成有关.对PMMA/SAN(60/40)体系,加入SiO2粒子后相分离温度上升,但并未改变相分离机理,仍为亚稳单相分解过程(spinodal decomposition,SD);而对于PMMA/SAN(30/70)体系,加入SiO2粒子后却降低了体系的相分离温度.该现象可能是SiO2粒子和基体组分界面间组成与PMMA/SAN共混物基体组成的差异造成的.     

HDPE-g-PB接枝共聚物的合成及其与聚丁二烯的共混

利用~(60)Co辐照合成了HDPE与丁二烯的接枝共聚物,PE-g-PB。动态力学试验表明,它与PB较PE与PB有更好的相容性。PB含量相同时PB/PE-g-PB共混物比PB/PE共混物有较高的抗张强度和断裂伸长率。前者中两相分布较均匀,相区尺寸较小。     

Upper critical solution temperature type phase behavior of poly(styrene‐co‐acrylonitrile) blends with poly(styrene‐co‐n‐phenyl maleimide) and their interaction energies

To enhance the heat resistance of poly(styrene‐co‐acrylonitrile‐co‐butadiene), ABS, miscibility of poly(styrene‐co‐acrylonitrile), SAN, with poly(styrene‐co‐n‐phenyl maleimide), SNPMI, having a higher glass transition temperature than SAN was explored. SAN/SNPMI blends casted from solvent were immiscible regardless of copolymer compositions. However, SNPMI copolymer forms homogeneous mixtures with SAN copolymer within specific ranges of copolymer composition upon heating caused by upper critical solution temperature, UCST, type phase behavior. Since immiscibility of solvent casting samples can be driven by solvent effects even though SAN/SNPMI blends are miscible, UCST‐type phase behavior was confirmed by exploring phase reversibility. When copolymer composition of SNPMI was fixed, the phase homogenization temperature of SAN/SNPMI blends was increased as AN content in SAN copolymer increased. To understand the observed phase behavior of SAN/SNPMI blend, interaction energies of blends were calculated from the UCST‐type phase boundaries by using the lattice‐fluid theory combined with a binary interaction model. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1131–1139, 2008     

Ternary blends of phenoxy/SAN/poly(-ε-caprolactone)

The compatibilizing effect of poly(ε-caprolactone) (PCL) on the blends of two immiscible polymers, poly(hydroxy ether of bisphenol A) (phenoxy) and poly(styrene-co-acrylonitrile) (SAN) has been investigated. The phase behavior of the ternary blends was affected by the AN content in the SAN copolymers and a maximum miscible region was observed at 19.5 wt % of AN. The effect of AN content on the phase behavior of the ternary blends was interpreted in terms of the relative magnitude of the segmental interaction energy densities, which were obtained by combining a melting point depression and an extended binary interaction model. When a small amount of PCL was added to the phenoxy/SAN blends, the phase morphology showed a finer phase dispersion, indicating that the interfacial tension between the phenoxy and SAN is considerably reduced. However, the improvement in tensile properties was limited despite the morphological change with the PCL content. From the results of the DSC measurements, SEM, and tensile testing, it was understood that the PCL acted as a compatibilizer for the immiscible phenoxy/SAN blends. © 1994 John Wiley & Sons, Inc.     

Modification of EVOH copolymers with ϵ‐caprolactone: synthesis and compatibilization effects in PE/PVC blends

Polyethylene‐polycaprolactone graft copolymers with different chemical structures (i.e. different number and length of PCL grafts and molecular weight of PE backbone) were synthesized from various EVOH copolymers and ϵ‐caprolactone, using Aluminum isopropoxide as catalyst, and were tested for their compatibilizing capability in PE/PVC blends. PE and PCL segments in the graft copolymers were found completely immiscible, while PCL segments of the graft copolymers were found completely miscible with PVC. When graft copolymers were added to PE/PVC blends they proved to be good agents for the dispersion of PVC phase in the PE matrix. SEM showed also improved adhesion between the dispersed PVC phase and PE matrix. Moderate improvements in mechanical properties were also observed in preliminary tensile tests.     

Transition from miscibility to immiscibility in blends of poly(methyl methacrylate) and styrene-acrylonitrile copolymers with varying copolymer composition: a DSC study

The glass transition and the structural relaxation processes have been studied in blends of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile (SAN) copolymers with different acrylonitrile (AN) contents. The 50/50 wt.% blend of PMMA with the SAN copolymer containing 30 wt.% of AN is immiscible, while blends with copolymers containing between 13 and 26 wt.% of AN are miscible. Thus the upper limit of miscibility is between 26 and 30 wt.% of AN. The temperature dependence of the relaxation times of the conformational rearrangements of polymer chains around the glass transition have been determined in the blends and pure components by modelling DSC thermograms obtained after different thermal histories in each sample. The slope in the Arrhenius diagram logτ vs 1/T around the glass transition temperature is significantly smaller in the blend which is closer to the upper limit of miscibility than in the other miscible blends in which SAN copolymer contains less AN. The change of slope can be ascribed to a distribution in the glass transition temperatures of the different rearranging regions, reflecting the appearance of a microheterogeneity in the blend that cannot be detected as a double glass transition in the blend.     

Morphology of Nylon-6 blends with styrenic polymers

The morphology of blends of styrenic polymers in a matrix of 75% Nylon-6 prepared in a Brabender Plasti-Corder was examined by scanning electron microscopy. Styrene/acrylonitrile copolymers (SAN) form smaller particles as the AN level increases owing to the corresponding decrease in the SAN–polyamide interfacial tension. Various styrenic polymers containing functional groups, maleic anhydride or oxazoline type, that can react with Nylon-6 during melt processing were added to the SAN phase which also led to a decrease in the particle size owing to the graft copolymer formed in situ. The effects of functional group type, amount of functional groups per chain, amount of functional polymer added, and the miscibility of the styrene/maleic anhydride (SMA) and SAN copolymers on the morphology of the styrenic phase in the Nylon-6 matrix are described. © 1992 John Wiley & Sons, Inc.     

EFFECT OF PLASTICIZER ON THE MICROSTRUCTURE OF PS/PVC BLENDS

In this work, controlling of the particle size of PVC in PS/PVC blends was studied. Itis shown that viscosity ratio and particle size can be changed by adding a third composition,such as plasticizers, and the distribution of the third composition in two phases plays avery important role in controlling viscosity ratio and particle size. When DOP was used asthe plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduceddue to the transference of DOP into PS phase. When polycaprolactone (PCL) was usedas the plasticizer of PVC in the same blends, the particle size of PVC could be descreasedobviously because PCL does not migrate to PS phase.     

Transition from crazing to shear deformation in ABS/PVC blends

ABS/PVC blends were prepared over a range of compositions by mixing PVC, SAN, and PB‐g‐SAN. All samples were designed to have a constant rubber level of 12 wt % and the ratio of total‐SAN to PVC in the matrix of the blends varied from 70.5/17.5 to 18/80. Transmission electron microscope and scanning electron microscope have been used to study deformation mechanisms in the ABS/PVC blends. Several different types of microscopic deformation mechanisms, depending on the composition of blends, were observed for the ABS/PVC blends. When the blend is a SAN‐rich system, the main deformation mechanisms were crazing of the matrix. When the blend is a PVC‐rich system, crazing could no longer be detected, while shear yielding of the matrix and cavitation of the rubber particles were the main mechanisms of deformation. When the composition of blend is in the intermediate state, both crazing and shear yielding of matrix were observed. This suggests that there is a transition of deformation mechanism in ABS/PVC blends with the change in composition, which is from crazing to shear deformation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 687–695, 2006     

异山梨醇型聚碳酸酯与ABS树脂共混体系的结构与性能研究

采用异山梨醇型聚碳酸酯(DB),与掺混型ABS熔融共混制备了具有不同聚丁二烯(PB)含量和丙烯腈(AN)含量的DB/掺混型ABS合金,并在考察掺混型ABS特征对合金结构与性能的影响的基础上,分别使用同种掺混型ABS以及各种商品化ABS树脂,比较了DB/ABS合金和双酚A型聚碳酸酯/ABS合金的性能及其变化规律.结果表明,对DB/掺混型ABS(70/30)合金而言,PB含量变化对于合金拉伸性能的影响明显大于AN含量变化所带来的影响,在PB含量为6.3 wt%条件下,各不同AN含量的合金体系均有最好的性能表现.PB含量和AN含量变化对合金分散相形态的影响与力学拉伸性能变化特征一致.DB/ABS合金体系均具有良好的热稳定性与热力学相容性,受AN含量和PB含量变化的影响较小,合金玻璃化转变温度与DB非常接近.以双酚A型聚碳酸酯为基础的聚碳酸酯(PC)/ABS合金及以异山梨醇型聚碳酸酯为基础的DB/ABS合金,在拉伸性能变化上均表现出完全相同的规律,且无论是采用掺混型ABS还是采用商品化ABS的体系,PC/ABS与DB/ABS合金在拉伸性能所反映出的规律也是基本一致的.     

Reactively and physically compatibilized immiscible polymer blends: stability of the copolymer at the interface

This paper reports on the interfacial behaviour of block and graft copolymers used as compatibilizers in immiscible polymer blends. A limited residence time of the copolymer at the interface has been shown in both reactive blending and blend compatibilization by preformed copolymers. Polystyrene (PS)/polyamide6 (PA6), polyphenylene oxide (PPO)/PA6 and polymethylmethacrylate (PMMA)/PA6 blends have been reactively compatibilized by a styrene-maleic anhydride copolymer SMA. The extent of miscibility of SMA with PS, PPO and PMMA is a key criterion for the stability of the graft copolymer at the interface. For the first 10 to 15 minutes of mixing, the in situ formed copolymer is able to decrease the particle size of the dispersed phase and to prevent it from coalescencing. However, upon increasing mixing time, the copolymer leaves the interface which results in phase coalescence. In PS/LDPE blends compatibilized by preformed PS/hydrogenated polybutadiene (hPB) block copolymers, a tapered diblock stabilizes efficiently a co-continuous two-phase morphology, in contrast to a triblock copolymer that was unable to prevent phase coarsening during annealing at 180°C for 150 minutes.     

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。