含无规共聚物三元共混体系SMMA-PMMA-SAN相行为

含无规共聚物共混体系的相容性研究正在成为近年来的研究热点 ,因为相容的驱动力来自共聚物分子内不同单体链段间的排斥性相互作用 [1～ 3] .目前研究这类体系还主要采用过份简化的 F- H平均场理论 ,用旨在克服平均场理论缺陷的 Flory状态方程 ( EOS)理论仅局限于研究二元共聚物共混体系[4～ 8] .与三元共混体系相比 ,用 EOS理论预测含两个无规共聚物三元体系相行为尚需确定共聚物 -共聚物间的二元参数 sj/si,Xij和 Qij.若用 Ax B1- x和 Cy D1- y分别代表共聚物 1和 2 ,则 A,B,C,D代表相应共聚物中的单体单元 ,x,y分别是 1和 2的共…     

用苯乙烯-丙烯腈无规共聚物作增容剂改善聚碳酸酯/聚甲基丙烯酸甲酯相容性的研究

对聚碳酸酯（ＰＣ）／苯乙烯 丙烯腈无规共聚物（ＰＳＡＮ）／聚甲基丙烯酸甲酯（ＰＭＭＡ）三元共混物，运用平均场理论，通过二元链段相互作用参数χｉｊ计算了其中三个二元对共混组成的相互作用参数χｂｌｅｎｄ，并计算了三元共混体系的ｓｐｉｎｏｄａｌ曲线．由此预测了三元共混物相容的条件，讨论了ＰＳＡＮ组成，各聚合物分子量对体系相容性的影响，并进行了实验验证．结果表明通过适当控制共聚组成和分子量，ＰＳＡＮ可以作为ＰＣ和ＰＭＭＡ共混物的增容剂，并可以通过仅改变ＰＳＡＮ在共混物中的比例来改善体系的相容性，直至得到完全均相的三元共混物．     

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.     

均聚物/共聚物共混体系的相行为研究进展

通过控制均聚物与共聚物共混过程中的相行为,能够得到许多性能优异的材料。本文从理论和实验两方面总结了影响均聚物／共聚物共混体系相容性和形态结构的因素,主要包括均聚物的分子量、浓度,共聚物的组成、结构、浓度,与均聚物相应的共聚物组分的分子量,共聚物分子内的相互作用,均聚物与共聚物分子间的相互作用等。     

分子间相互作用对聚肽共聚物/聚苯乙烯衍生物共混体系自组装形貌影响的研究

合成了两亲性的聚(γ-苄基-L-谷氨酸酯)-b-聚乙二醇(PBLG-b-PEG)聚肽刚-柔嵌段共聚物和聚苯乙烯(PS)均聚物及多种聚苯乙烯衍生物,包括聚(4-乙酰氧基苯乙烯)(PAS)均聚物、聚(4-羟基苯乙烯)(PVPh)均聚物和聚(苯乙烯-co-4-乙酰氧基苯乙烯)(P(S-co-AS))共聚物.用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H-NMR)和凝胶渗透色谱(GPC)等表征了聚合物的结构、分子量及分布.采用共溶剂溶解、选择性溶剂透析的方法,制备了PBLG-b-PEG嵌段共聚物与不同PS衍生物(包括PS均聚物)共混体系的自组装聚集体,利用透射电子显微镜(TEM)和扫描电子显微镜(SEM)等表征了自组装体的形貌和结构.研究发现,不同的分子间相互作用(如π-π共轭作用、偶极-偶极相互作用、氢键作用等)对共混体系的自组装形貌有显著的影响.PBLG-b-PEG/PS共混体系自组装可形成表面具有条纹结构的"毛线球"聚集体,该体系中PBLG和PS之间形成π-π共轭作用,相互作用强度相对较弱;PBLG-b-PEG/PAS共混体系自组装可形成表面基本光滑并有轻微凹陷的球形聚集体,该体系中PBLG和PAS之间除了π-π共轭作用,还可形成相对较强的偶极-偶极相互作用;而PBLG-b-PEG/PVPh共混体系自组装得到了囊泡,该体系中PBLG与PVPh之间可形成π-π共轭和氢键作用,相互作用强度进一步增强.对于PBLG-b-PEG/P(S-co-AS)共混体系,可通过改变P(S-co-AS)共聚物中AS摩尔分数和制备温度来调控自组装聚集体表面的条纹形貌.根据PBLG链段与不同PS衍生物(包括PS均聚物)之间不同的分子间相互作用,提出了上述聚集体形貌转变的机理.     

聚碳酸酯与苯乙烯-丙烯腈共聚物共混体系相容性及其对光学性能的影响

利用分子内链段排斥性相互作用理论研究了聚碳酸酯 (PC) 苯乙烯 丙烯腈共聚物 (SAN)共混体系中组份分子量及SAN共聚比例对体系相容性的影响规律 ,确定了获得均相的PC SAN共混体系的条件 ,考察了体系相容性与光学性能之间的关系 .通过实验获得了均相的PC SAN共混物 ;研究结果表明PC聚合度为 90、SAN聚合度为 3 0的PC SAN(S体积含量为 68%)体系共混比在 60∶40附近时体系的双折射能够实现补偿 ,紫外透光率达到 70 %.     

聚氧化乙烯-聚苯乙烯-聚氧化乙烯三嵌段共聚物/聚苯醚共混物的相容性和结晶行为

本工作对聚氧化乙烯-聚苯乙烯-聚氧化乙烯(PEO-PS-PEO)三嵌段共聚物与聚苯醚(PPO)均聚物共混物的相容性及结晶行为进行了研究。结果表明,共混体系的相容性与嵌段共聚物中苯乙烯段的含量有关,PS含量越高,PPO与共聚物PS段的相容性越好。共混体系的结晶行为也明显不同于一般均聚物共混体系。在DSC降温结晶过程中最多可出现三个结晶峰。     

聚氧化乙烯-聚苯乙烯-聚氧化乙烯三嵌段共聚物/聚苯醚共混物的相容性和结晶行为

 本工作对聚氧化乙烯-聚苯乙烯-聚氧化乙烯(PEO-PS-PEO)三嵌段共聚物与聚苯醚(PPO)均聚物共混物的相容性及结晶行为进行了研究。结果表明,共混体系的相容性与嵌段共聚物中苯乙烯段的含量有关,PS含量越高,PPO与共聚物PS段的相容性越好。共混体系的结晶行为也明显不同于一般均聚物共混体系。在DSC降温结晶过程中最多可出现三个结晶峰。     

玻璃基板作用下高分子共混物薄膜相形态发展过程

研究了玻璃基板作用下极性高聚物为低组分的共混物薄膜在退火条件下相形态的发展过程 .选用聚苯乙烯 (PS) 聚甲基丙烯酸甲酯 (PMMA)与聚苯乙烯 (PS) 聚ε 己内酯 (PCL)两个体系 ,在玻璃基板上Spin Coating成膜后退火 .由于共混物薄膜中极性相对较大的高聚物组分 (PMMA和PCL)相对于极性较小的PS组分对玻璃基板具有更好的润湿性 ,所以在上述的两个共混薄膜体系中其相形态分别显示PMMA和PCL在低组分比例下最终发展成为连续相 .利用扫描电镜以及元素分析很好地验证了以上的结论 ,并且对其机理进行了解释 .此外 ,改变PS的分子量与PCL共混 ,研究了组分粘度对薄膜相形态发展的影响 .结果表明 ,PS组分粘度越大 ,共混物薄膜相结构发展速度越慢     

含氢键高分子共混体系的分相动力学研究

经过共聚改性的含羟基聚苯乙烯PS(OH)可以和许多含质子接受基团的聚合物形成氢键而成为互溶体系,本文着重研究这类含氢键共混体系的相分离动力学以及它们的相图。PS(OH)是由苯乙烯与对-六氟异丙醇-α-甲基苯乙烯共聚得到。它与聚甲基丙烯酸丁酯PBMA组成的共混物用温度跃变光散射法研究分相动力学行为。分相初期,符合Cahn-Hilliard-Cook线性理论,共混物具有LCST性质。由于PS(OH)中只含有1.5mol%OH基团,使得共聚物的组成不均匀,以及PS(OH)和PBMA的分子量多分散性,导致共混物的临界共溶点不在亚稳单相极限线(Spinodal curve)和稳定单相极限线(Binodal Curve)的最低点。对于临界组成的共混物在分相后期相区的增长按Siggia模型进行。而非临界组成的共混物按Lifshitz-Slyozov模型进行而且散射光强I(q,t)随散射矢量q的变化出现与q无关的峰,这与金属氧化物的共混物有类似的情况。     

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.     

Influence of Competition Between Binary Pairwise Interactions on the Phase Behavior in Ternary Blends

There are three binary pairs in a ternary blend and competition exists among these pairwise interactions owing to the asymmetry of the interaction energies between these binary pairs, which will determine the overall phase behavior of the blend. The influence of molecular weight of the components on the asymmetry of the interactions was discussed based on a ternary copolymer blend poly(styrene-co-acrylonitile)/poly(styrene-comethylmethacrylate/poly(methyl methacrylate-co-acrylonitile) (SAN/SMMA/MAN). It has been demonstrated that the asymmetry of the interactions between different binary polymer pairs is driven not only by the difference of interaction parameters, i.e. the so-called Δξ effect, but also by the difference of chain length between different components in the mixture. If the two effects are coincident with each other, the asymmetry of the interactions will be intensified, promoting phase separation. On the other hand, the compatibility of the system may be improved remarkably as the two factors are in opposite directions. It implies that a miscible ternary blend may be available simply by exchanging the order of the molecular weight between the different components against the asymmetry direction caused by their corresponding interaction parameters, which is easier to do in many experimental conditions. © 1997 John Wiley & Sons, Ltd.     

Morphology and grafting reactions in core/shell latexes

The particle morphology and percent grafting were investigated as a function of the crosslink density of the seed latex in two systems of core/shell latexes of polybutadiene/polymethyl methacrylate (PB/PMMA) and styrene–butadiene rubber/polymethyl methacrylate (SBR/PMMA) prepared by seeded emulsion polymerization at 50°C. The thin layer chromatography/flame ionization detection (TLC/FID) technique was used to characterize the grafting efficiency of the core/shell latexes. The percent grafting of the shell polymer was found to decrease with increasing the crosslink density of the core material. The particle morphology and precent grafting were also investigated as a function of composition and structure of the core material in four core/shell latex systems: polybutadiene/styrene–acrylonitrile copolymer (PB/SAN), (styrene-butadiene) random copolymer/styrene acrylonitrile copolymer (S:B/SAN), polystyrene : polybutadiene/styrene-acrylonitrile copolymer (PS:PB/SAN) and Kraton/styrene-acrylonitrile copolymer (Kraton/SAN), which were prepared by direct emulsification for the seed followed by emulsion polymerization at 70°C for the shell polymer. Grafting and crosslinking of the core material were found to be competitive reactions depending on the microstructure of the seed latex.     

Conductivity of Poly(methyl methacrylate)/Polystyrene/Carbon Black and Poly(ethyl methacrylate)/Polystyrene/Carbon Black Ternary Composite Films

Poly(methyl methacrylate)(PMMA)/polystyrene(PS)/carbon black(CB)and poly(ethyl methacrylate)(PEMA)/PS/CB ternary composite films were obtained using solution casting technique to investigate double percolation effect.In both PMMA/PS/CB and PEMA/PS/CB ternary composite films,the CB particles prefer to locate into PS phase based on the results of calculating wetting coefficient,which is also confirmed by SEM images.The conductivity of the films was investigated,and the percolation threshold(￠c)of both ternary composite films with different polymer blend ratios was determined by fitting the McLachlan GEM equation.Conductivity of PMMA/PS/CB ternary composite films showed a typical double percolation effect.However,due to the double emulsion structure of PEMA/PS polymer blends,the PEMA/PS/CB ternary composite films(PEMA/PS=50/50)showed a higher￠c,even CB only located in PS phase,which conflicts with the double percolation effect.A schematic diagram combined with SEM images was proposed to explain this phenomenon.     

Shear flow effect on phase behavior and morphology in polymer blends

The effect of simple shear flow on the phase behavior and morphology was investigated for both polystyrene/poly(vinyl methyl ether) (PS/PVME) and poly(methyl methacrylate)/poly(styrene‐co‐acrylonitrile) (PMMA /SAN‐29.5) blends, which have LCST (lower critical solution temperature)‐type phase diagram. The measurements were carried out using a special shear apparatus of two parallel glass plates type. The PS/PVME blends showed shear‐induced demixing and shear‐induced mixing at low and high shear rate values, respectively. In addition, the rotation speed and the sample thickness were found to have a pronounced effect on the phase behavior under shear flow. On the‐other hand, PMMA/SAN blend showed only shear‐induced mixing and the magnitudes of the elevation of the cloud points were found to be composition and molecular weight dependent. The morphology of the PMMA/SAN=75/25 blend indicated that shear‐induced mixing occurred at a critical shear rate value, below which the two phases were highly oriented and elongated in the flow direction.