PVC/PBD-b-PMMA共混体系相容性的研究

采用ＤＭＡ和ＴＥＭ系统研究了聚丁二烯－聚甲基丙烯酸甲酯的嵌段共聚物（ＰＢＤ－ｂ－ＰＭＭＡ）与聚氯乙烯（ＰＶＣ）共混体系的相容性问题。结果表明：ＰＶＣ／ＰＢＤ－ｂ－ＰＭＭＡ共混体系具有部分相溶性。相容的程度与共混体系的组成、组分聚合物的分子量以及共聚物中ＰＢＤ和ＰＭＭＡ嵌段的比例密切相关。     

致孔剂对HP（MA—VAc—MMA）载体孔结构的影响

以二乙烯苯和双丙烯酸多缩乙二醇酯为交联剂、聚醋酸乙烯酯（ＰＶＡｃ）或它与醋酸丁酯（ＢＡＣ）的混合物为致孔剂、ＢＰＯ为引发剂，用悬浮聚合随后水解的方法制得了部分水解聚（丙烯酸甲酯－醋酸乙烯酯－甲基丙烯酸甲酯）［ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）］多孔载体，研究了ＰＶＡｃ及（ＰＶＡｃ＋ＢＡＣ）用量、分子量及混合比对ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）孔结构的影响。结果表明，当ＰＶＡｃ的Ｍ＞２．５×１０５，ＰＶＡｃ／ＢＡＣ为２．３，用量为１０～２０％时，可制得孔隙率较高，孔径分布较窄，孔表面积较大的多孔载体。这种载体适用于微生物固定化。     

醋酸纤维素／聚乙烯基吡咯烷酮共混体系的相容性研究（Ⅰ）

用ＤＳＣ，ＤＭＴＡ研究了醋酸纤维素（ＣＤＡ），聚乙烯基吮咯烷酮（ＰＶＰ）及ＣＤＡ／ＰＶＰ共混体系的玻璃化转变行为．用精密量热法测定了该体系的混合热焓．结果表明：共混体系只存在一个玻璃化转变温度（Ｔｇ），其值随共混组成的变化而改变；共混体系的混合热焓为负值，其绝对值随组成中ＰＶＰ含量的增加而减少．力学性能研究表明，共混体系具有协同效应．上述试验结果证明，ＣＤＡ和ＰＶＰ是一对相容性高聚物．     

POM／EVA共混物的研究

用力学测试、扫描电镜（ＳＥＭ）、热分析（ＤＳＣ）等手段研究了聚甲醛（ＰＯＭ）与乙烯－醋酸乙烯酯共聚物（ＥＶＡ）共混物（ＰＯＭ／ＥＶＡ）的力学性能及其微同形态；用聚甲醛与马来酸二丁酯（ＤＢＭ）的接枝物（ＰＯＭ－ｇ－ＤＢＭ）作相溶剂，能改变共的两相间的粘结力，从而提出了共混物的力学性能，ＳＥＭ观察表明接枝物的加入改变了ＰＯＭ／ＥＶＡ共混物的断裂方式，微观形态及结晶性能，对其热性能影响不大；通过改变ＰＯ     

醋酸纤维素／聚乙烯基吡咯烷酮共混体系的相容性研究（Ⅰ）

 用ＤＳＣ，ＤＭＴＡ研究了醋酸纤维素（ＣＤＡ），聚乙烯基吮咯烷酮（ＰＶＰ）及ＣＤＡ／ＰＶＰ共混体系的玻璃化转变行为．用精密量热法测定了该体系的混合热焓．结果表明：共混体系只存在一个玻璃化转变温度（Ｔｇ），其值随共混组成的变化而改变；共混体系的混合热焓为负值，其绝对值随组成中ＰＶＰ含量的增加而减少．力学性能研究表明，共混体系具有协同效应．上述试验结果证明，ＣＤＡ和ＰＶＰ是一对相容性高聚物．     

乳液共聚反应过程与聚合物结构关系及~（13）C－NMR对聚合物结构的表征

用间歇法和半连续法进行了丙烯酸丁酯（ＢｕＡ）与醋酸乙烯酯（ＶＡｃ）乳液共聚合．１３Ｃ－ＮＭＲ对共聚产物分子结构测试表明，在间歇法共聚合中随着反应进行其组成及结构发生很大变化，而半连续法确能制得成份及结构均匀一致的Ｐ（ＢｕＡ－ＶＡｃ）共聚物．由于ＢｕＡ水溶性小于ＶＡｃ，而其竟聚率远大于ＶＡｃ，间歇法共聚合反应初期只有少量ＶＡｃ参加共聚合．通过对间歇法共聚合中不同反应时间聚合物的１３Ｃ－ＮＭＲ测试，表明反应初期聚合的ＶＡｃ以单链节或二元序列形式存在于主要由ＢｕＡ单元构成的分子链中，而并未形成较长ＶＡｃ链段．对上述试样玻璃化转变温度的测试结果与１３Ｃ－ＮＭＲ实验结果颇为一致．     

二胺扩链剂对RIM聚氨酯－脲弹性体的结构与性能的影响

采用实验室小型ＲＩＭ机制备了一组不同芳香二胺扩链的嵌段聚氨酯－脲（ＰＵＵ）弹性体，借助于ＩＲ、ＤＳＣ、ＤＭＴＡ、ＳＥＭ以及拉伸试验等测试手段对其结构与性能进行了研究．通过比较由ＭＤＡ、ＤＥＴＤＡ以及ＣＡＭＤＡ三种不同活性和结构的芳香二胺扩链剂与二异氰酸酯反应形成的硬链段对ＲＩＭＰＵＵ弹性体的结构与性能的影响，表明：ＭＤＡ基ＲＩＭＰＵＵ中软、硬链段微区界面作用指数很小，微相分离程度却很大，其性能最差；ＤＥＴＤＡ基ＲＩＭＰＵＵ弹性体有理想的界面作用指数，以及适当的微相分离程度，其性能位于三者之中最佳．ＤＭＴＡ研究证实在一定的温度范围内ＤＥＴＤＡ基ＲＩＭＰＵＵ的模量稳定性最好．     

高橡胶含量透明MBS合成及其对PVC的改性

高橡胶含量透明ＭＢＳ合成及其对ＰＶＣ的改性高南，肖贵斌，胡伟军（上海大学化学系上海嘉定２０１８００）关键词　ＭＢＳ树脂，ＰＶＣ树脂，乳液聚合，塑料增韧，透射电镜ＭＢＳ（甲基丙烯酸甲酚－丁二烯－苯乙烯）树脂具有复杂的多相结构，可用作硬质聚氯乙烯（ＰＶＣ...     

核／壳结构聚丙烯酸酯增韧剂改性PVC的研究

用核／壳结构聚丙烯酸酯增韧剂对ＰＶＣ进行了抗冲击改性，研究了增韧剂的组成结构与增韧效果之间的关系，通过实验发现在本工作所考察的范围内，增韧剂粒径越大，其增韧效果越好．电镜观察证实共混体系的形态为弹性体粒子均匀地分散在ＰＶＣ基体中．     

PVC／SBR／MBS三元共混合金的研究

对ＰＶＣ／ＳＢＲ／ＭＢＳ三元共混合金作了研究。在ＰＶＣ／ＳＢＲ体系中加入ＭＢＳ，ＰＶＣ的冲击强度可提高５．５倍，弯曲强度的保留率在８０％左右。电镜和ＤＤＶ测试表明ＭＢＳ的加入提高了ＳＢＲ对ＰＶＣ的相容性，增强了橡胶对ＰＶＣ的界面粘结力。     

含环氧基的丙烯酸酯共聚物改性环氧树脂

合成了一系列含环氧基团的丙烯酸酯聚合物（ＨＧＭＢ），并对其改性环氧树脂／４，４‘－二氨基二苯基甲烷的抗冲性能，动态力学行为进行了考察，结果表明：当必性体系中加入质量分数为１５％的ＨＧＭＢ（甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙基酯、甲基丙烯酸甲酯、丙烯酸丁酯的摩尔分数分别为４．３％、５％、２５．７％、６５％）时，与空白体系相比，改性体系的冲击强度提高５０％，且玻璃化有所提高，模量没有降低。     

PVC与核壳结构聚丙烯酸酯及环氧树脂的共混增韧

研究发现由分段乳液聚合丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯制备的三层核壳结构共聚体和少量环氧树脂(含固化剂及促进剂)与PVC在适当配比下共混,可使改性PVC的抗冲击性能明显提高。考察了共混体系的组成与其冲击强度及断裂形态之间的关系。     

Silicone‐based impact modifiers for poly(vinyl chloride), engineering resins,and blends

Silicone‐based impact modifiers were prepared in a previous study. The modifiers were composed of silicone/acrylic rubber cores and grafted acrylic shells. They improved the toughness of poly(vinyl chloride) (PVC) and poly(methyl methacrylate). The silicone emulsion that was used to produce the silicone‐based impact modifiers was prepared via two routes: emulsion polymerization and bulk polymerization of octamethyltetracyclosiloxane. Many silicone‐based impact modifiers were produced that had different silicone/acrylic rubber characteristics. Through a toughness examination of modified PVC, the best composition of the silicone‐based impact modifiers was obtained, and the silicone content in the rubber composition was 25 wt %. The morphology of the silicone‐based impact modifiers, determined by transmission electron microscopy, was as follows: core and second shell polymers were mainly poly(butyl acrylate), and the first shell polymer was silicone. The silicone‐based impact modifiers were blended with engineering resins such as PVC, polycarbonate (PC), poly(butylene terephthalate) (PBT), and PC/PBT mixtures. The impact strength under standard conditions and after weathering test conditions for blends of the silicone‐based impact modifiers were investigated with respect to two commercially available acrylic and methyl methacrylate/butadiene/styrene impact modifiers. The results showed good weatherability and good toughness under low‐temperature conditions for the silicone‐based impact modifiers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1112–1119, 2004     

Morphology and fracture behavior of toughening‐modified poly(vinyl chloride)/organophilic montmorillonite composites

Toughening‐modified poly(vinyl chloride) (PVC)/organophilic montmorillonite (OMMT) composites with an impact‐modifier resin (Blendex 338) were prepared by melt intercalation, and their microstructures were investigated with wide‐angle X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy. The mechanical properties of the PVC composites were examined in terms of the content of Blendex and OMMT, and the fracture toughness was analyzed with a modified essential work of fracture model. Intercalated structures were found in the PVC/OMMT composites with or without Blendex. Either Blendex or OMMT could improve the elongation at break and notched impact strength of PVC at proper contents. With the addition of 30 phr or more of Blendex, supertough behavior was observed for PVC/Blendex blends, and their notched impact strength was increased more than 3319% compared with that of pristine PVC. Furthermore, the addition of OMMT greatly improved both the toughness and strength of PVC/Blendex blends, and the toughening effect of OMMT on PVC/Blendex blends was much larger than that on pristine PVC. Blendex and OMMT synergistically improved the mechanical properties of PVC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 286–295, 2004     

Modified suspension‐PVC particles as absorbents of ortho‐dichlorobenzene from water

Modified porous PVC particles are studied as absorbents of o‐dichlorobenzene (DCB), from water. The modified particles were produced by an in‐situ stabilizer‐free polymerization/crosslinking of a monomer/crosslinker/peroxide solution absorbed within commercial porous suspension‐type PVC particles. The modifying monomers used include styrene with divinyl benzene (DVB) as a crosslinking comonomer, methyl methacrylate (MMA), butyl acrylate (BA), or ethylhexyl acrylate (EHA) with ethylene glycol dimethacrylate (EGDMA) as a crosslinking comonomer. The effect of the nature of the monomers, morphology, porosity, surface area and composition of the modified PVC particles on DCB absorption was studied. Batch experiments (absorption rate and isotherms) were used to screen the PVC absorbents on the basis of absorption rate and absorption capacity. Continuous absorption column experiments were conducted to study the parameters characterizing the absorption process. Both the unmodified and modified PVC particles absorb DCB from water. The PBA and PEHA‐modified PVC particles approach equilibrium capacity faster and have greater absorption capacity than neat PVC, PS‐modified PVC and PMMA‐modified PVC particles. The absorption characteristics are influenced by the modifying polymer's T_g. The rubbery nature of PBA and PEHA yields better absorption in spite of the significantly lower surface area and porosity obtained in the modified PVC particles. Thus, indicating that fast adsorption followed by bulk absorption of DCB is taking place. A clear influence of the crosslinking effect was not established. The continuous absorption experiments were found more efficient than the batch absorption experiments. Copyright © 2003 John Wiley & Sons, Ltd.     

Permanently antistatic and high transparent PMMA terpolymer: Compatilizer,antistatic agent,and the antistatic mechanism

Permanently antistatic and high transparent PMMA terpolymer, P(MMA‐co‐HPA‐co‐SPMA), were reported in this paper, providing a new method to significantly improve the antistatic properties of PMMA without sacrificing transparency. 2‐Hydroxypropyl acrylate (HPA) was chosen as a kind of compatilizer because of the good compatibility with both methyl methacrylate (MMA) and sulfopropyl methacrylate potassium salt (SPMA), a potential antistatic agent with a strong hydrophilic group. The mechanical and optical properties of P(MMA‐co‐HPA‐co‐SPMA) terpolymer barely show any visibly differences compared to PMMA homopolymer, confirmed through Fourier transform infrared, dynamic mechanical analysis, and a haze meter. Furthermore, antistatic property analysis indicates that only a small amount of SPMA can significantly improve the antistatic properties of the obtained PMMA terpolymers. The surface resistivity of the P(MMA‐co‐HPA‐co‐SPMA) sheets could be reduced to 10⁹ Ω sq⁻¹ order of magnitude, while the SPMA content reached 0.72 wt%. The hydrophilic groups, the hydroxyl and acrylate sulfonate, on the surface contributed to attract the water molecules, which rendered it a reasonably good antistatic property. These selected terpolymers will provide more opportunities to develop high‐performance and antistatic products made from PMMA materials.     

Hydrophobically associating water‐soluble polymers; a dramatic growth of solution viscosity and the specificity of physical gel formation

The rheological properties of dilute and semidilute solutions (viscosity) and physical gels (elasticity modulus) of hydrophobically modified self‐associated binary polymers (formed by micellar polymerization of acrylamide and methyl methacrylate with side hydrophobic groups (HG) containing 9, 12 and 18 C‐atoms), and terpolymers (the same monomers and a charged component — sodium acrylate) are studied. The dependences of properties on the length, form (linear or branched) and the number of HG and charges is established. It is shown that a very small number of linear HG leads to a considerably higher solution viscosity, starting at a smaller concentration compared with the effects of a larger number of branched HG. Solutions of terpolymers of concentration 2–3 wt % form physical gels that are thixotropic. After dilution, the polymers suddenly form gels at certain concentrations without the preliminary stage of viscosity growth     

聚氯乙烯/聚丙烯酸丁酯/白泥纳米复合材料的研究

通过多步交换反应及扩散－聚合的方法,使聚丙烯酸丁酯被嵌入到改性层状结构的白泥层间,得到白泥－聚丙烯酸丁酯纳米复合物的微米粒子;然后将聚氯乙烯与白泥－聚丙烯酸丁酯进行熔融共混,制得具有一一特性的有机－无机纳米复合材料,并对复合材料的缺口冲击强度及动态力学性能进行了研究,结果表明,白泥－聚丙烯酸酯含量为5．0wt％时,复合材料的力学性能最佳;聚氯乙烯与高含量的白泥－聚丙烯酸丁酯（分别为25．0wt%和50．0wt%）形成的复合材料,在聚氯乙烯的玻璃化转变温度之前,储能模量出现先降低而后增加的过程。     

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.     

P(BA-EHA)/PVC复合胶乳的制备及表征

采用乳液聚合法合成了丙烯酸丁酯与丙烯酸 2 乙基己酯交联共聚物 [P(BA EHA) ]乳液 ,以P(BA EHA)乳液为种子通过与氯乙烯 (VC)聚合制备了P(BA EHA) PVC复合胶乳 .考察了P(BA EHA)乳液用量对复合胶乳粒径及其材料力学性能的影响 ,借助透射电镜 (TEM)、扫描电镜 (SEM)和动态力学分析 (DMA)等手段对复合胶乳粒子及其所制材料的形态结构进行了表征 .DMA研究结果表明 ,橡胶相P(BA EHA)与基体PVC间相容性得到了良好改善 .随着P(BA EHA)含量的增加 ,低温区材料的力学损耗峰较纯聚氯乙烯增强 ,且峰位逐渐向高温区移动 .TEM照片显示 ,复合胶乳粒子具有清晰的核壳结构 ;P(BA EHA)非常均匀地分散在PVC中 ,两相界面模糊 .由SEM照片可见 ,材料缺口断面表现为很好的韧性断裂 .含 4 2 %P(BA EHA)材料的缺口抗冲强度是PVC的 11倍 ,断裂伸长率较PVC提高近两倍 .