苯乙烯/聚氯乙烯接枝膜的热稳定性研究

用自由基悬浮聚合法合成了苯乙烯 /聚氯乙烯接枝膜 ,并对产物热处理 ,然后进行紫外 -可见光谱 ,红外光谱 ,热失重分析。结果表明接枝苯乙烯后的聚氯乙烯膜热稳定性得到了提高。同时 ,讨论了热稳定性机理。     

等离子体引发聚丙烯接技苯乙烯共聚物的合成及性能

将等离子体接枝技术用于聚丙烯接枝苯乙烯共聚物的合成．ＦＴ ＩＲ、ＳＥＭ及ＸＰＳ证明所得产物为接枝共聚物．研究了不同等离子体处理体系压强、处理功率，反应瓶不同直径、体积，不同接枝聚合反应时间、温度对接枝率的影响．利用接枝共聚物制备了硫酸钠型离子交换膜，并对其电性能进行了初步探讨．     

聚偏氟乙烯溶液法接枝苯乙烯磺酸膜的结构与形貌研究

以过氧化苯甲酰(BPO)作引发剂，通过溶液接枝聚合法把苯乙烯接枝到碱处理过的聚偏氟乙烯(PVDF)膜上，磺化后得到聚偏氟乙烯接枝苯乙烯磺酸(PVDF-g-PSSA)电解质膜。研究发现碱处理过的PVDF膜更容易与苯乙烯发生接枝聚合反应，且接枝率与碱处理时间呈线性变化关系。用红外光谱、差示扫描量热法检测PVDF膜经过接枝以及随后的磺化所发生的膜结构变化，并用SEM观察PVDF膜接枝前后以及接枝磺化后产物PVDF-g-PSSA膜的形貌及硫分布。研究表明，用KOH碱处理过的PVDF膜与苯乙烯进行接枝共聚反应时，PVDF膜结构在接枝前后和磺化前后发生变化，说明苯乙烯确实接枝到PVDF膜上。     

苯乙烯/马来酸酐和苯乙烯/甲基丙烯酸二甲氨基乙酯二元体系在聚四氟乙烯多孔膜上的γ辐射接枝

在氮气的氛围下用γ辐照的方法在聚四氟乙烯多孔膜上接枝苯乙烯 马来酸酐、苯乙烯 甲基丙烯酸二甲氨基乙酯二元单体 .并且研究了剂量、剂量率、溶液中单体的浓度和二元单体的摩尔比等条件对接枝率的影响 .探讨了两种单体的竞聚率对接枝率、接枝膜的组成及性能的影响 .结果表明 ,苯乙烯 马来酸酐二元体系对接枝率有协同效应 ,苯乙烯 甲基丙烯酸二甲氨基乙脂二元体系对接枝率表现为加合效应 .制备的二元接枝的聚四氟乙烯多孔膜可以进一步磺化来制备用于质子交换膜燃料电池的质子交换膜 .     

改性聚偏氟乙烯接枝磺化聚(苯乙烯-co-丙烯酸)膜的研制

以过氧化苯甲酰(BPO)作引发剂,通过溶液接枝聚合法把苯乙烯/丙烯酸同时接枝到原硅酸钠改性的聚偏氟乙烯(PVDF)膜上,磺化后得到聚偏氟乙烯接枝磺化聚(苯乙烯-co-丙烯酸)膜(PVDF-g-P(SSA-co-AA)).研究了苯乙烯和丙烯酸的不同比例对膜的接枝反应及其相对湿度对膜电导率和含水量的影响.用傅立叶变换红外光谱(FTIR)检测原硅酸钠改性的PVDF膜经过接枝和磺化后所发生的结构变化,并用扫描电镜(SEM)观察PVDF膜接枝前后的形貌以及接枝磺化后产物PVDF-g-P(SSA-co-AA)膜的形貌及硫和硅分布.结果表明,原硅酸钠改性的PVDF膜与苯乙烯/丙烯酸同时发生接枝聚合反应,环境的相对湿度在20%～80%范围,对添加10wt%Na4SiO4的PVDF-g-P(SSA-co-AA)膜的电导率的影响基本不变,并达到0.0198S·cm-1.原硅酸钠改性的PVDF膜结构在接枝前后和磺化前后发生变化,确认磺化反应不只是在膜表面,同时渗入膜中进行.     

改性木薯淀粉/橡胶复合材料的制备及性能研究

以木薯淀粉、马来酸酐、苯乙烯为原料,过硫酸钾为引发剂,通过溶液共聚合成了一系列苯乙烯改性淀粉树脂(SMS)。然后将改性淀粉同丁苯橡胶(SBR)、天然橡胶(NR)进行混炼、硫化模压成型,制得苯乙烯改性淀粉/丁苯橡胶/天然橡胶复合材料。采用红外光谱(IR)对苯乙烯改性淀粉接枝共聚物进行了结构表征。通过拉伸性能测试考察了不同苯乙烯含量的木薯淀粉接枝产物对丁苯橡胶/天然橡胶的力学性能的影响。结果表明,淀粉改性后,随着苯乙烯含量的增多,所得复合橡胶的拉伸强度与邵氏硬度均呈现先增加后降低的趋势。当苯乙烯用量为15%时所制得的苯乙烯改性淀粉/丁苯橡胶/天然橡胶复合材料的拉伸强度与邵氏硬度最大且优于未改性淀粉复合材料,其拉伸强度为2.0MPa,邵氏硬度为25.8HD。     

改性聚偏氟乙烯接枝共混聚苯乙烯磺酸膜的制备与性能

将苯乙烯添加到溶有原硅酸钠改性的聚偏氟乙烯(PVDF)N-甲基吡咯烷酮溶液中, 以过氧化苯甲酰(BPO)作引发剂, 苯乙烯直接接枝到原硅酸钠改性的PVDF链上, 成膜后磺化制备了聚偏氟乙烯接枝苯乙烯(PVDF-g-PSSA)膜. 采用傅立叶变换红外光谱(FT-IR)、扫描电镜(SEM)、能量扩散X射线(EDX)和多功能材料实验机表征了膜的结构、形貌及硫和硅的分布、机械强度、溶胀度, 使用阻抗分析和气相色谱仪研究了苯乙烯含量(w)对PVDF-g-PSSA膜的质子导电性能和阻醇性能的影响. 结果表明, 苯乙烯加入后, 原硅酸钠改性的PVDF与苯乙烯进行接枝共聚反应, 苯乙烯磺化反应不只是在膜表面进行, 同时渗入到膜中进行, 机械性能得到了改善. 质子电导率(σ)随苯乙烯质量分数的提高而升高. Na4SiO4为8%和苯乙烯为20%的PVDF-g-PSSA膜, 在25 ℃时溶胀度仅为20.4%, 甲醇透过系数在10-7 cm2·s-1数量级上, 比Nafion115膜的低一个数量级. 该膜具有较高的选择性, 在直接甲醇燃料电池中具有良好的应用前景.     

聚四氟乙烯辐射接枝苯乙烯-丙烯酸的研究

本文采用共辐照工艺,在20°—40℃范围内研究了聚四氟乙烯辐射引发接枝苯乙烯-丙烯酸的动力学。找到了接枝温度与临界辐照强度的关系。高于临界辐照强度,接枝发生在表面,反之,接枝发生在整体。借光学显微镜和扫描电子显微镜研究了接枝膜的断面和表面结构。表面接枝膜的接枝量约1毫克/厘米~2,平均粘结强度高达100公斤/厘米~2以上。表面接枝膜的电性能与未接枝的聚四氟乙烯相仿。可知聚四氟乙烯表面辐射接枝苯乙烯-丙烯酸可用作强粘结强度的结构材料或电子元件的粘结密封材料。     

聚氨酯与接枝乙烯基酯树脂互穿网络研究: 自由基共聚 单体的影响

通过分子设计技术合成了两种侧链种类和长度可能控制的接枝乙烯基酯树脂(VER),并用它们与聚氨酯(PU)形成了同步互穿网络(SIN)。通过DSC,SEM,TEM,FTIR等考察了接枝VER的共聚单体对VERSIN的形态结构与力学性能的影响。研究结果表明,用甲基丙烯酸甲酯(MMA)为共聚单体的接枝VER网络中的MMA链段与PU网络中的硬段有较好的相容性,导致这类PU/接枝VERSIN中两个网络间的相容性和互穿程度好于由苯乙烯为共聚单体时合成4SIN。因此,在这两类共聚单体合成的SIN中,由MMA形成的接枝VER网络增强PU网络的效果更为显著。     

聚全氟乙丙膜电子束引发预辐射接枝AA和SSS制备阳离子交换膜的研究

利用电子束引发预辐射接枝技术,在聚全氟乙丙烯(FEP)薄膜上接枝丙烯酸(AA)和对苯乙烯磺酸钠(SSS),制备一种含羧酸基团和磺酸基团的阳离子交换膜,详细研究了反应温度、单体总浓度、pH值变化、辐照气氛及添加剂对接枝率的影响规律,明确了实验条件与接枝率的对应关系。FTIR测试证明了接枝产物是全氟乙丙烯和丙烯酸、对苯乙烯磺酸钠的接枝共聚物。     

原子转移自由基聚合法合成大豆分离蛋白-g-聚甲基丙烯酸2-羟乙酯

通过酰胺化反应在大豆分离蛋白(SPI)表面引入溴原子,合成了大分子引发剂SPI-Br,以CuCl和bpy为催化体系,通过原子转移自由基聚合法(ATRP)合成了大豆分离蛋白-g-聚甲基丙烯酸2-羟乙酯(SPI-g-PHEMA).用FTIR1、3C-NMR、GPC对大分子引发剂、接枝产物和接枝物降解链进行结构表征.结果表明,得到了表面接枝聚甲基丙烯酸2-羟乙酯长链的大豆分离蛋白接枝聚合物,用紫外分光光度计(UV)、荧光分光光度计z、eta电位和透射电镜(TEM)表征了接枝产物的溶液性质和微观形态.     

Thermally responsive graft copolymer of soy protein isolate and N-isopropylacrylamide: synthesis and self-assembly behavior in aqueous solution

In recent years, soy protein isolate (SPI) has attracted great attention due to its biodegradability, biocompatibility, and wide availability. It has been used in food and pharmaceutical industry such as edible films and drug delivery systems. In this study, we report the synthesis and self-assembly behavior in aqueous solution of thermally responsive graft copolymer (SPI-g-poly(N-isopropylacrylamide) (PNIPA)) of soy protein isolate and N-isopropylacrylamide in aqueous solution. SPI-g-PNIPA was synthesized in the 8 mol/l urea cushioning solution, by using ammonium persulfate as the initiator and mercaptoacetic acid as the protein unfolding agent. Laser light scattering, transmission electron microscopy, and fluorescence spectroscopy have been used to study the self-assembly behavior of SPI-g-PNIPA in aqueous solution. Above the critical micelle concentration (cmc), SPI-g-PNIPA aggregates could assemble into different structures including the simple spherical structure, spherical core–shell structure, and random coil structure, depending on the graft copolymer concentration. The graft copolymer concentration, temperature, pH value, and ionic strength were found to influence the aggregate size and morphology of SPI-g-PNIPA in aqueous solution. With increasing ionic strength, the aggregate size increases. However, pH value, SPI-g-PNIPA concentration, and temperature have complicated influences on the aggregate size. The lower critical solution temperature of the SPI-g-PNIPA at pH 8.5 is 36 °C. The method of intrinsic fluorescence spectroscopy was used for the first time to determine the cmc value of SPI-g-PNIPA in aqueous solution.     

Thermal properties of polyfurfuryl alcohol absorbed/adsorbed on arylated soy protein films

In this study, polyfurfuryl alcohol was absorbed/adsorbed on soy protein isolate films by immersing the SPI films in acid-catalysed furfuryl alcohol solution for 60 h followed by complete curing at 145–150 °C for 2 h. PFA absorbed/adsorbed soy protein films designated as SPI-PFA were then arylated in the presence of 0.5% (w/v) 2,2-diphenyl-2-hydroxyethanoic acid for 4 h to fabricate arylated soy protein films designated as SPI-PFA-Ar. The incorporation of PFA and introduction of aromatic backbone through arylation is revealed from Fourier transform infrared study. Thermal studies of SPI, SPI-PFA and SPI-PFA-Ar were carried out by thermogravimetric analysis, differential scanning calorimetry and dynamic mechanical thermal analysis. In addition, mechanical properties, surface morphology and water uptake of all the three different types of the films were evaluated. Results indicated that PFA absorbed/adsorbed arylated soy protein films showed higher thermal stability than native SPI films.     

Deposition of polymer latices on grafted Nylon 6 fiber

Deposition of polymer latices on a grafted Nylon 6 fiber was studied as a function of pH and the degree of grafting. The latices were polystyrene (PS), styrene/acrylamide copolymer (P(St/AAm)) and styrene/acrylic acid copolymer (P(St/AA)). The deposition of the latices on the grafted fiber decreased in every case with increasing pH and no deposition was observed at alkaline pH. The grafting of fiber with acrylic and methacrylic acid reduced the deposition of P(St/AAm) and P(St/AA) latices but had no influence on the deposition of PS latex. The relation between the deposition rates and the interaction energy at acidic pH indicates that the deposition of PS latex on the grafted fiber mainly depends on the electrostatic interaction. These results suggest that the expansion of water-soluble polyelectrolyte layer on the surface of grafted fiber plays an important role on the deposition.     

Effects of calcium carbonate polymorph on the structure and properties of soy protein-based nanocomposites

Novel protein-based nanocomposites were well prepared by in vivo synthesis and co-precipitation of soy protein isolate (SPI) with calcium carbonate (CaCO3) in an aqueous solution. The resultant CaCO3 in the nanocomposites was identified as calcite- and aragonite-type, respectively. The morphology and structure of the CaCO3/SPI composites were investigated by means of wide-angle X-ray diffraction, Fourier transform infrared spectra, scanning electron microscopy, and high-resolution transmission electron microscopy. The results revealed that the polymorph and the size of CaCO3 in the nanocomposites were dependent on its content, pH, and the conformation of soy protein. At the content of more than 5%, CaCO3 was changed into calcite crystal with the preference of growing along (104) plane. However, at lower content of less than 5%, CaCO3 preferred to form aragonite in the composite as a result of the modulation by soy protein. The aragonite nanocrystals were arrayed in the direction of (111) plane and self-assembled along beta-sheet planes of soy protein polypeptides. The mechanical properties, thermal stability, and water resistance of the CaCO3/SPI nanocomposites were significantly improved as a result of the nanosized effects. Interestingly, the aragonite/SPI nanocomposite exhibited higher tensile strength (about 50 MPa) than that of calcite/SPI, owing to a good compatibility and strong interaction between aragonite and soy protein polypeptides. This work provided a simple pathway to develop the soy protein-based bio-hybrid materials with high mechanical strength and valuable information on their structure-properties relationship.     

Properties and biodegradability of water-resistant soy protein/poly(?-caprolactone)/toluene-2,4-diisocyanate composites

Water-resistant composite plastics were prepared from soy protein isolate (SPI) or soy dreg (SD), poly(?-caprolactone) (PCL) and toluene-2,4-diisocyanate (TDI) as the compatibilizer by blending and one-step reactive extrusion (REX) followed by compression-molding. The structure and properties of the materials (SPI series and SD series) were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, dynamic mechanical thermal analysis and tensile testing. The results indicated that SPI and SD series exhibited high water resistance and good tensile strength (14.8 MPa for SPI35 and 16.3 MPa for SD35). Moreover, the SD series sheets containing cellulose possessed higher tensile strength than those of SPI series when SD content was 30-35%, whereas the latter had a better biodegradability and water resistance. By burying the two series of sheets in soil and culturing them in a mineral salt medium containing microorganisms, both of them were almost completely degraded. This paper provides a convenient way to prepare new soy protein plastics with good biodegradability and water resistivity.     

Properties stability and biodegradation behaviors of soy protein isolate/poly (vinyl alcohol) blend films

The objective of this work was to investigate the color, transparency, water sensitivity and mechanical properties stability in air under photo-oxidative degradation influencing consumer acceptance and biodegradation behaviors in soil of soy protein isolate (SPI)/poly (vinyl alcohol) (PVA) blend packaging films during 30 days. The results showed that PVA could dilute the yellow color and make the SPI-based films less darkness in application and the transparency of SPI/PVA films at various stages of degradation was improved. The addition of PVA decreased the ability of SPI protein molecules to absorb water and enhanced the mechanical properties of blend films comparing to pure SPI film in 30 days. Aerobic biodegradation of films in soil proved that the PVA compound interacting with protein imposed negative effects on biodegradation of blend films prolonging their decomposing time. The SPI/PVA blend films decomposed into small fragments of less complex molecules along with surface completely digested after 30 days.     

聚苯乙烯/蒙脱土纳米复合材料的制备及结构研究

以可与苯乙烯发生共聚的阳离子表面活性剂乙烯苄基二甲基十八烷基氯化铵(VOAC)为插层处理剂改性蒙脱土(VC18-MMT),有机蒙脱土在超声波强剪切作用以及乳化剂作用下预分散在乳化剂溶液中,然后引入苯乙烯单体进行原位乳液聚合制备聚苯乙烯/蒙脱土纳米复合材料.采用XRD和TEM对纳米复合材料的结构进行了表征.结果表明,绝大多数的蒙脱土被剥离成单个片层均匀的分散在聚合物基体中;动态力学分析表明,纳米复合材料的储能模量和玻璃化温度均有所增加,而动态损耗有所降低;接枝在蒙脱土片层上的聚合物通过与锂离子进行阳离子交换反应提取下来,采用GPC和NMR对接枝聚合物的结构进行了表征,结果表明,接枝聚合物是较基体分子量低且分布很宽的苯乙烯和乙烯苄基二甲基十八烷基氯化铵的共聚物,计算表明每一个共聚物分子链上平均含有大约25个乙烯苄基二甲基十八烷基氯化铵分子.     

Synthesis of copolymer brushes endowed with adhesion to stainless steel surfaces and antibacterial properties by controlled nitroxide-mediated radical polymerization

Novel copolymer brushes have been synthesized by a two-step "grafting from" method that consists of the electrografting of poly(2-phenyl-2-(2,2,6,6-tetramethyl-piperidin-1-yloxy)-ethylacrylate) onto stainless steel, followed by the nitroxide-mediated radical polymerization of 2-(dimethylamino ethyl)acrylate and styrene or n-butyl acrylate, initiated from the electrografted polyacrylate chains. The grafted copolymers were quaternized in order to endow them with antibacterial properties. Peeling tests have confirmed the strong adhesion of the grafted copolymer onto the stainless steel substrate. Quartz crystal microbalance experiments have proven that fibrinogen adhesion is lower on the hydrophilic quaternized films compared to the nonionic counterpart. Such quaternized copolymers exhibit significant antibacterial activity against the Gram-positive bacteria S. aureus and the Gram-negative bacteria E. coli.     

Enzymatically modified Soy Protein

Optimum temperature and pH for the isolation of soy protein isolate (SPI) from soy protein concentrate (SPC) were established. Enzymatic hydrolysis of SPI with enzymes of different specificities such as trypsin, chymotrypsin, papain and urease was carried out and the products of hydrolysis were characterized by molecular mass determination [sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE)] and thermal techniques [differential scanning calorimetry (DSC) and thermogravimetric analysis (TG)]. Enzymatic hydrolysis resulted in a significant reduction in molecular masses. However the thermal stability of hydrolysed SPI was similar to native SPI indicating that it is independent of molecular mass. DSC studies indicated an increase in temperatures of endothermic transition associated with SPI denaturation and loss of absorbed moisture in samples of lower molecular masses. This revised version was published online in August 2006 with corrections to the Cover Date.