ESBS嵌段共聚物的制备及反应机理研究

利用甲酸和过氧化氢原位生成的过氧甲酸对苯乙烯-丁二烯-苯乙烯（SBS）嵌段共聚物进行环氧化,制备了环氧化SBS（ESBS）。采用FT—IR、GPC、TGA和MFR对ESBS进行了表征,分析了环氧化反应机理。结果表明,在环氧化反应过程中,SBS分子链上聚丁二烯链段1,4-结构中C=C双键的反应活性要大于1,2-结构中C=C双键的反应活性。当反应时间较长时,ESBS会发生环氧基开环副反应。在SBS的环氧化反应初期,会有部分分子链发生断裂生成小分子产物,反应后期会发生环氧基或C=C双键引发的分子间偶联反应,容易形成交联不溶物。     

Synthesis of amphiphilic graft copolymers of SBS with acrylamide and study of their properties

Graft copolymerization of SBS in the form of sodium ionomer with acrylamide in emulsion using benzoyl peroxide as initiator and sodium ionomer of maleated SBS as a self‐emulsifier, which can form a stable cyclohexane/water emulsion with AM without using any other emulsifier, was carried out. Factors affecting the graft copolymerization were studied. The grafting % can reach about 15%. Emulsifying properties of sodium ionomer of maleated SBS and the graft copolymer, as well as the compatibilizing effect of the graft copolymer in blending polyvinyl chloride (PVC) with SBS, were studied. The sodium ionomer of maleated SBS, the graft copolymers, and the blends were characterized with IR and DSC. The results showed that water absorbency and emulsifying volume increase obviously after graft copolymerization with AM. 0.2 g of the graft copolymer containing 14 wt % PAM grafts can emulsify a mixture of 30 mL toluene and 70 mL water completely. The graft copolymer can be used as an effective compatibilizer in the blending of PVC and SBS, more effective than the sodium ionomer of maleated SBS. Only 2 wt % of the copolymer based on the blend used in blending is enough to raise the tensile strength three times. The blends with weigh ratios of PVC/SBS at 3/7–4/6 in the presence of the graft copolymer behave as thermoplastic elastomers with a tensile strength of 14 MPa, an ultimate elongation of 750%, and a permanent set of 17%. Glass transition temperatures of the blend shifted inward in the presence of the graft copolymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1248–1253, 2005     

聚碳酸酯-g-聚苯乙烯共聚物的合成与表征

研究了聚碳酸酯（ＰＣ）与苯乙烯（ＳＴ）的悬浮接枝共聚合,考察了ＰＣ／ＳＴ质量比、引发剂质量分数、反应时间对共聚合的影响,获得了接枝率为３５％,接枝效率为６５％的接枝共聚物,并对接枝共聚物进行ＩＲ、ＤＳＣ、ＤＭＡ等表征,测定了支链ＰＳ的分子量及支链数。     

辐射接枝SBS的性能研究

采用旋转流变仪研究了苯乙烯-丁二烯-苯乙烯（sgs）嵌段聚合物接枝α-甲基丙烯酸（MAA）、甲基丙烯酸甲酯（MMA）接枝共聚物（SBS-g-MAA，SBS-g-MMA）的动态流变性能。结果表明：接枝共聚物的黏流活化能降低，温度敏感性降低；比较改性前后的共聚物的主曲线，接枝共聚物的相对分子质量分布变宽，在剪切应力作用下，黏度下降较快；接枝共聚物的相对分子质量分布变宽，接枝共聚物的抗氧化性增强。     

聚苯乙烯-聚硅氧烷接枝共聚物的合成与表征

以甲基丙烯酰氧丙基聚硅氧烷大单体(PDMS-MA)与苯乙烯共聚合,制备了聚苯乙烯-聚硅氧烷梳状接枝共聚物（PSt-g-PDMS）,采用傅里叶变换红外光谱（FTIR）表征了接枝共聚物的组成,研究了聚硅氧烷大单体的相对分子质量对共聚合活性的影响,并对接枝共聚物的热性能进行了表征.结果表明,大单体PDMS-MA的共聚合活性随其相对分子质量的增大而减小,随投料比的增加,共聚合转化率下降.与纯聚苯乙烯相比,PSt-g-PDMS的热稳定性提高.而且,随着大单体PDMS-MA相对分子质量和它在共聚物中含量的增加,接枝共聚物的热稳定性增加.     

SBS与醋酸乙烯酯本体接枝物的合成

以过氧化苯甲酰为引发剂,醋酸乙烯酯为溶剂,在无氮气保护下,合成得到了主链为SBS支链为PVAC的接枝共聚物SBS-g VAC,其结构被红外光谱所证实;讨论了引发剂、时间、温度及SBS用量对接枝反应的影响。     

Homogeneous Photoinouced Graft Copolymerization of Acrylamide onto Abs Copolymers in the Presence of 4-Acetyldiphenyl as Photosensitizer.: 1. Influence of Butadiene Content in Abs Copolymers

Photoinduced graft copolymerization of acrylamide (AM) onto two types of acrylonitrile-butadiene-styrene (ABS) copolymers was extensively investigated in homogeneous media. The grafting process was conducted in chloroform in presence of 4-acetyldi-phenyl (4-AD). Ultraviolet (UV) irradiation was used in the range of 310 to 460 nm. The UV spectrum of 4-AD has sλ_max at 285 nm and shows n-π^? transitions. The grafting parameters, such as weight conversion, grafting percentage, and grafting efficiency, were determined as a function of the irradiation time and the concentrations of monomer, initiator, and substrate. A reverse effect was observed between the grafting percentage and the butadiene content in ABS copolymers. The rates of graft copolymerization of AM onto the two types of ABS copolymers were determined. A Trommsdorf effect was observed in certain systems. The IR spectrum of ABS-g-AM graft copolymer shows the appearance of a new peak at 1685 cm^-1 that declares the presence of poly-acrylamide-grafted chains onto the ABS copolymer backbone. A probable copolymerization mechanism was proposed.     

聚(丙烯酸-丙烯酰胺)接枝辛基酚聚氧乙烯醚丙烯酸酯两亲性共聚物的合成及表征

以辛基酚聚氧乙烯醚丙烯酸酯(C8PhEO10Ac)为大分子单体,丙烯酸(AA)、丙烯酰胺(AM)为共聚单体,采用大分子单体接枝共聚法,制备了一种两亲性接枝共聚物(AA-AM-g-C8PhEO10Ac),用静态光散射(SLS)与GPC联用技术测得接枝共聚物的分子量为9.51×105,用FTIR、1H NMR和TG/DTA等手段对共聚物的结构及性能进行了表征。采用透射电子显微镜(TEM)对聚合物在水溶液中的自组装行为进行了初步研究。结果表明,AA-AM-g-C8PhEO10Ac在水溶液中自组装,形成球型胶束,随着浓度增大,趋向于形成更大的自组装体。     

双亲性氯化聚乙烯接枝共聚物的吸水膨胀性能

采用反相悬浮法制备了颗粒状接枝共聚物———氯化聚乙烯接枝丙烯酸(CPE-g-AA)、氯化聚乙烯接枝丙烯酰胺(CPE-g-AM)和氯化聚乙烯接枝混合单体丙烯酸、丙烯酰胺[CPE-g-(AA-AM)],并通过热压法制得接枝共聚物片材。考察了颗粒状接枝共聚物和接枝共聚物片材的吸水膨胀性能。结果表明,接枝共聚物的吸水性能与接枝单体的种类及其接枝率有关,相同接枝率的CPE-g-AA的吸水量比CPE-g-AM的大。当混和单体丙烯酸/丙烯酰胺的质量比为2/2时,所得接枝共聚物的抗盐性能最好。接枝共聚物片材可反复吸水膨胀,接枝率为62%的CPE-g-AA片材的二次吸水达到平衡时的吸水率和膨胀率分别为120%和41%。通过测定接枝共聚物的接触角表明,CPE-g-AA对水的润湿作用比CPE-g-AM明显。     

Synthesis,characterization, and self‐assembly of amphiphilic fluorinated gradient copolymer

An amphiphilic copolymer of acrylic acid (AA) and 2,2,2‐trifluoroethyl methacrylate (TFEMA) was synthesized by reversible addition‐fragmentation transfer (RAFT) copolymerization, using a feed method for adding TFEMA. The kinetics of the RAFT copolymerization agreed well with those characteristic of a first‐order reaction and the molecular weight of copolymers increased with the conversion increasing, both demonstrating that it proceeded in a controlled polymerization manner. Optimal copolymerization was achieved when the reaction was conducted at 70°C, using a molar ratio of TFEMA : AA : RAFT agent : initiator of 400 : 400 : 4 : 1. Analysis of instantaneous ¹H‐NMR results proved that the obtained copolymer had a chain structure with AA segments gradually changing to TFEMA segments. The copolymer films had lower surface free energies and slightly microphase separation structures. The amphiphilic copolymer with gradient structures could self‐assemble to form aggregates in selective solvents. The type and composition of solvent mixtures had great effects on the morphology and sizes of aggregates, which were investigated by transmission electron microscopy and dynamic light scattering, respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci., 2013