Synthesis and characterization of polyurethane/poly(vinylidene chloride) interpenetrating polymer networks

A series of polyurethane (PU)/poly(vinylidene chloride) (PVDC) interpenetrating polymer networks (IPNs) were synthesized through variations in the amounts of the prepolyurethane and vinylidene chloride monomer via sequential polymerization (80/20, 60/40, 50/50, 40/60, 30/70, and 20/80 PU/PVDC). The physicomechanical and optical properties of the IPNs were investigated. Thermogravimetric analysis (TGA) studies of the IPNs were performed to establish their thermal stability. TGA thermograms showed that the thermal degradation of the IPNs proceeded in three steps. Microcrystalline parameters, such as the crystal size and lattice disorder, of the PU/PVDC IPNs were estimated with wide‐angle X‐ray scattering. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1375–1381, 2007     

双酚单丙烯酸酯类抗氧剂GM的合成

以2,2′-甲撑双(4-甲基-6-特丁基苯酚)(简称2246)、丙烯酸、氯氧化磷等为反应原料,通过酯化反应合成了GM,考察了合成GM的适宜工艺条件。在n(2246)∶n(丙烯酸)∶n(氯氧化磷)=1∶1.25∶0.90、催化剂m(三乙胺)∶m(2246)=1∶1.0X、反应温度105℃、反应时间2.5 h的合成条件下,原料2246转化率大于96.0%;GM产品选择性大于91.0%;GM产品摩尔收率大于83.0%;GM产品的液相色谱纯度大于99.0%。采用该工艺合成抗氧剂GM的特点是将酰卤化过程和脱卤化氢过程合二为一,由2246和丙烯酸直接进行酯化反应合成GM。工艺流程短,产品收率高、质量稳定,有可能便于工业化生产。     

In situ observation of methoxide hydrogenation on the Ni(111) surface

The surface chemistry of methoxide (CH₃O-) on the Ni(111) surface has been studied in the presence of hydrogen pressures up to 2 Torr. During heating in vacuum methoxide decomposes to H₂ and CO, which desorb at 380 and 445 K, respectively. The CH₃O-decomposition process is rate limited by CH bond breaking and exhibits a strong deuterium kinetic isotope effect in CD₃O-. In the presence of ambient hydrogen pressures of 0.02–2.0 Torr both CH₃O- and CD₃O-are hydrogenated directly to methanol at 310 K. Methoxide is hydrogenated by adsorbed hydrogen, which nearly saturates the surface at these pressures and temperatures.     

D102的Ti(OC_2H_5)_4杂化材料的制备与性能研究

采用Sol-Gel法制备了D102的Ti(OC2H5)4杂化材料,探讨了材料的制备工艺条件,对材料进行了表面形态,热性能,光学性能等测试和分析。结果显示透光性和热稳定性较纯有机功能分子D102都有所提高,薄膜表面平整,无相分离。     

碳四烃催化裂解制丙烯反应过程中尾气分析

采用2阀2柱HP6890气相色谱运行系统,通过HPPLOT/Al2O3"S"毛细管柱分析有机烃类,并用FID检测,13 X分子筛填充柱分析氢气,用TCD检测,建立了碳四烃催化裂解制丙烯反应尾气分析方法。结果表明:标准样品的分析结果标准偏差不大于4%,实际样品测试结果可保障物料平衡在98%以上。     

采用DSC和FTIR对木材和API胶粘剂间反应的研究

采用差示扫描星热法(Differential Scanning Calormelry,简称DSC)和傅立叶变换红外吸收光谱(Fourier Transform Infrared Spectroscopy,简称FTIR)对木材和水性高分子异氰酸酯胶粘剂(Aqueous Polymer Isocyanate,简称API)的胶接机理进行了研究。DSC和FTIR的试验结果均表明:API胶粘剂和木材间发生了化学反应:API胶粘剂和木材间发生的反应所需活化能远小于API胶粘剂的主剂+固化剂的活化能,亦即用API 胶粘剂胶接木材时发生的反应要比API胶粘剂本身的固化反应容易得多,同时从理论上证明使用API胶粘剂胶接木材时装配时间最长不应超过其活性期的一半时间,且装配时间越短越好;文中还研究了升温速率对API胶粘剂DSC图谱的影响。     

Free‐radical grafting of acrylic acid onto isotactic polypropylene using styrene as a comonomer in supercritical carbon dioxide

Free‐radical grafting of acrylic acid (AAc) onto isotactic polypropylene (iPP) using styrene (St) as a comonomer in supercritical carbon dioxide (SCCO₂) medium was studied. The effects of temperature and pressure of reaction on functionalization degree (grafting degree of AAc) of the products were analyzed. The increase of reaction temperature increases the diffusion of monomers and radicals in the disperse reaction system of SCCO₂. In addition, the increase of temperature accelerates the decomposition rate of 2,2′‐azobisisobutyronitrile (AIBN), thus promoting grafting reaction. It was also observed that functionalization degree of the products decreases with the increase of pressure of SCCO₂ in the range of experiment. The effects of comonomer St on the functionalization degree of the products were investigated. The AAc graft degree of the resulting polymer was drastically higher in the present of St. It reached a maximum when the mass ratio of St and AAc was about 0.7 : 1. Because AAc is not sufficiently reactive toward iPP macroradicals, it would be helpful to use a second monomer that can react with them much faster than AAc. St preferentially reacts with the iPP macroradicals to form more stable styrene macroradicals, which then copolymerize with AAc to form branches. The highest functionalization degree was obtained when the AIBN was 0.75 wt %. When the initiator was used excessively, the functionalization degree decreased because of severe chain degradation of the iPP backbone. The morphologies of pure iPP and grafted iPP are different under the polarizing optical microscope. The diameter of the pure iPP spherulites is 20–38 μ and that of the grafted iPP spherulites is reduced with the increase of the functionalization degree of the products. This is proposed to be because the polar grafts formed during the reaction would have a tendency to associate in the hydrophobic PP environment. This might preserve some of the local crystalline order that existed during the reaction in the swollen iPP phase. It can be proven by a DSC cooling investigation that the crystallization temperature increased as the functionalization degree increased. This is proposed to be because the side‐chain of grafting polymer helps to bring about the heterogeneous nucleation in grafting polymer. Therefore, a large number of nuclei can emerge to a lesser supercooling degree. It can be also proven that the percent crystallization decreased as the functionalization degree increased, probably due to the grafted branches, which disrupted the regularity of the chain structure and increased the spacing between the chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2203–2210, 2004     

多孔氧化铝模板法制备取向碳纳米管阵列的研究进展

利用化学气相沉积技术在多孔氧化铝模板上可以制备取向碳纳米管阵列。通过调节阳极氧化参数可以改变模板的孔结构,进而可控制碳纳米管在孔道中生长的形貌。用这种方法制备的碳纳米管的直径、长度和密度可以选择性控制,这将有利于研究碳纳米管的性质和它在电化学及其他领域的应用。介绍了多孔氧化铝模板的形成原理以及碳纳米管在多孔氧化铝模板上的生长机理,讨论了阳极氧化条件、催化剂和气相沉积温度对碳纳米管特性的影响,并指出了这种技术中一些需深入研究的问题。     

Synthesis and characterization of soluble (porphyrinato)iron(II) polymers

The use of (tetrakis(4-hexylphenyl)porphyrinato)Fe(II) in polymerization reactions with bidentate ligands such as 9,10-diisocyanoanthracene and 1,4-diisocyanobenzene led to well-defined stacked polymers1 and2 which are still soluble in common organic solvents such as chloroform, dichloromethane, and tetrahydrofurane. They have been completely characterized by¹H-NMR and UV/vis spectropscopy in solution, even allowing end-group analysis for determination of the average degree of polymerization, yieldingn=10 andn=5 for1 and2, respectively. Mößbauer and IR spectroscopy further established the strong Fe-CN bonding reflected by very small isomer shifts and quadrupole splittings (E _Q0.2 mm s^–1) and a large decrease in the IR stretching frequency (v _CN60 cm^–1). The axially stacked polymers exhibit semiconducting properties only upon doping.Presented at the 5th International Symposium on Macromolecule-Metal Complexes (MMV), Summer 1993 in Bremen, Germany.     

人乳头瘤病毒16型晚期蛋白L1基因重组MVA病毒的构建及鉴定

目的研制预防人乳头瘤病毒(HPV)感染的重组修饰的Ankara痘病毒(MVA)活载体疫苗。方法将HPV16L1基因插入MVA病毒转移载体psc11M2的P7·5启动子的下游,构建转移质粒psc11M2-L1,与MVA共转染鸡胚成纤维细胞(CEF),进行同源重组。通过9轮蓝斑筛选,以PCR和Westernblot鉴定重组病毒。结果获得的含目的片段的重组MVA病毒,表达产物与鼠抗人HPV16L1抗体发生阳性反应,目的蛋白相对分子质量约为55000。结论已成功地构建了可正确表达HPV16L1基因的重组MVA病毒株。