Improving thermal and ozone stability of skim natural rubber by diimide reduction

The physical, chemical and thermal properties of diene-based polymers are improved by a chemical modification method such as hydrogenation. Skim natural rubber (SNR) which is mainly comprised of cis-1,4-polyisoprene was hydrogenated by diimide reduction in latex form, using hydrazine and hydrogen peroxide with copper sulfate as catalyst. The effect of various parameters on the level of hydrogenation calculated from proton nuclear magnetic resonance spectroscopy (¹H NMR) was investigated. The kinetic results indicated that the diimide hydrogenation of skim natural rubber latex (SNRL) exhibited a first order behavior with respect to the CC concentration. The apparent activation energy of the catalytic and non-catalytic hydrogenation of SNRL was calculated as 9.5 and 21.1 kJ/mol, respectively. From the TEM micrograph of hydrogenated SNRL particles, non-hydrogenated rubber core and hydrogenated rubber layer were observed according to a layer model. The results from thermal analysis confirmed that thermal stability of hydrogenated SNR was improved compared with the starting SNR. In addition, the thermal aging and ozone resistance of vulcanized hydrogenated SNR blends were also investigated.     

高填充量碳纳米管/丁苯粉末橡胶机械混炼的物理化学机制

将用喷雾干燥法制备的碳纳米管(CNTs)/丁苯粉末橡胶复合材料在开炼机上机械混炼, 考察机械混炼对复合材料常规力学性能的影响, 并对机械混炼对CNTs增强丁苯橡胶复合材料力学性能的影响进行相应的理论研究和机理分析. 结果表明, 与混炼前的复合材料相比, 机械混炼有效地提高了CNTs/丁苯橡胶复合材料的力学性能, 特别是当CNTs加入量较大时, 提高幅度更为显著, 与填充传统补强剂CB复合材料相比, 具有较大的优势. 这是因为机械混炼一方面使CNTs在橡胶基体中获得了更为充分均匀的分散; 另一方面, 混炼过程中产生的自由基以及巨大的剪切力, 使得CNTs与橡胶基体间界面结合如物理吸附、氢键作用、化学结合等得到了进一步增强, 提高了CNTs/丁苯橡胶复合材料的结合橡胶含量, 更好地发挥了CNTs对丁苯橡胶的补强效应, 从而提高了复合材料的拉伸强度和撕裂强度等力学性能. CNTs补强丁苯橡胶复合材料力学性能的机理符合“强键和弱键学说”.     

Interaction of zinc oxide clusters with molecules related to the sulfur vulcanization of polyolefins ("rubber")

The vulcanization of rubber by sulfur is a large‐scale industrial process that is only poorly understood, especially the role of zinc oxide, which is added as an activator. We used the highly symmetrical cluster Zn₄O₄ (T_d) as a model species to study the thermodynamics of the initial interaction of various vulcanization‐related molecules with ZnO by DFT methods, mostly at the B3LYP/6‐31+G* level. The interaction energy of Lewis bases with Zn₄O₄ increases in the following order: CO62H₄3H₆2S₂<1,4‐C₅H₈2O2S3N?CH₃COO^?. The corresponding binding energies range from ?57 to ?262 kJ mol^?1. However, Brønsted acids react with the Zn₄O₄ cluster with proton transfer from the ligand molecule to one of the oxygen atoms of Zn₄O₄, and these reactions are all strongly exothermic [binding energies [kJ mol^?1] in parentheses: H₂O (?183), MeOH (?171), H₂S (?245), MeSH (?230), C₃H₆ (?121), and CH₃COOH (?255)]. The important vulcanization accelerator mercaptobenzothiazole (C₇H₅NS₂, MBT) containing several donor sites reacts with the Zn₄O₄ cluster with proton transfer from the NH group to one of the oxygen atoms of ZnO, and in addition the exocyclic thiono sulfur atom and the nitrogen atom coordinate to one and the same zinc atom, resulting in a binding energy of ?247 kJ mol^?1. A second isomer of [(MBT)Zn₄O₄] with a strong O? H???N hydrogen bond rather than a Zn? N bond is only slightly less stable (binding energy ?243 kJ mol^?1). The NH form of free MBT is 36 kJ mol^?1 more stable than the tautomeric SH form, while the sulfurized MBT derivative benzothiazolyl hydrodisulfide C₇H₅NS₃ (BtSSH) is most stable with the connectivity >CSSH.     

合成润滑油的研究现状及发展趋势

润滑油作为机械运行不可缺少的材料,对维持机构的运行及提高机械寿命起到非常关键的作用.随着现代工业的不断进步,对机构运行寿命的要求越来越高,同时运行环境也越来越苛刻,这些均要求所采用的润滑油具有更为优异的综合性能.前期所采用的矿物基润滑油在耐温性、润滑性、抗氧化性、黏温性能等方面已经很难满足使用要求,因此需要采用合成润滑油.由于合成油采用人工合成的方式,其综合性能远高于普通矿物油,但目前合成油种类较多,不同种类的润滑油具有不同的性能及使用要求,因此本文介绍了常见的几种合成润滑油的国内外现状,并对合成润滑油的未来发展趋势进行了讨论和展望.     

有机硅改性磺酸型聚氨酯/丙烯酸酯复合乳液的制备

将磺酸型聚酯多元醇、异佛尔酮二异氰酸酯（IPDI)和三羟甲基丙烷(TMP)在无有机溶剂参与的情况下进行预缩聚,以硅烷偶联剂γ-氨丙基三乙氧基硅烷（KH550）作为改性剂,加入双官能团单体甲基丙烯酸-β-羟乙酯(HEMA),得到含乙烯基和有机硅封端的聚氨酯作为种子乳液,然后与甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)混合单体共聚,合成了有机硅改性磺酸型聚氨酯/丙烯酸酯复合乳液。 红外光谱的表征确定了有机硅改性磺酸型聚氨酯/丙烯酸酯复合乳液的化学结构;透射电子显微镜观察证实了此复合乳液具有明显的核壳结构;热重分析表明,经有机硅和丙烯酸酯改性后,胶膜的最大热失重温度提高了20 ℃,X射线衍射分析表明胶膜的结晶度降低,有利于提高膜的韧性。 力学性能测试及吸水率测试结果表明,当有机硅含量为1.9%时,胶膜的拉伸强度最高达到25.03 MPa,断裂伸长率为328%,此时膜的吸水率最低。     

顶空吸附萃取-气相色谱法分析小麦中部分风味物质

采用顶空吸附萃取法(headspace sorptive extraction, HSSE)建立了小麦中部分风味物质的分析方法。以硅橡胶为原料,采用溶胶-热空气硫化法,在模具中定型制得硅橡胶萃取棒。萃取棒的硅橡胶层体积约为87 μL,热稳定性好,耐热温度达到390 ℃。萃取棒吸附的风味物质经自制热解吸装置热脱附,被吹扫进入气相色谱仪进行分析。考察了萃取温度及时间、相比、热解吸条件对该方法萃取效率的影响。在优化条件下分析小麦粉标准样品,结果表明:方法的线性关系良好(r>0.9979),检出限为0.09～1.00 μg/kg,标准物质的平均添加回收率为95%～121%,相对标准偏差在2.2%～7.8%之间。对小麦粉实际样品进行分析,采用外标法得到了7种风味物质的绝对含量。该方法简便快捷,检出限低,适用于小麦中风味物质的快速定量分析。     

一类高折射率光固化有机硅树脂的性能研究

光固化有机硅材料兼具光固化的高效、能耗低和环保以及有机硅树脂优异的耐温、耐候性和电绝缘性能,因此,在LED等电子器件封装方面受到广泛关注.本文研究了自制的3种含丙烯酸酯基团的光固化苯基有机硅预聚物KDS-10、KMDS-03和KMS-03的光固化特性、光学性能和热稳定性能.结果表明,这些有机硅预聚物的折光指数随苯环含量的增加而增高,苯环含量从22.3%到37.7%,折光指数相应从1.496到1.542;3种预聚物与多种丙烯酸酯相容性好,用双官能的TPGDA作稀释剂,固化反应速率最快,丙烯酸酯基团的转化率也最高;光引发剂TPO引发的光固化反应速率和转化率均最高;高折射率有机硅预聚物KDS-10光固化后的薄膜具有优异的光学性能,在550 nm处的透过率为92.54%;玻璃化转变温度约为-17.41℃,起始分解温度为385℃.     

一种高折光率发光二极管封装硅树脂的研制

将甲基苯基二氯硅烷(MePhSiCl₂)与二甲基二氯硅烷(Me₂SiCl₂)、 甲基乙烯基二氯硅烷(MeViSiCl₂)和苯基三氯硅烷(PhSiCl₃)等共水解后, 在KOH催化下共缩聚, 以三甲基氯硅烷(Me₃SiCl)为封端剂, 制备了含有甲基苯基硅氧链节的甲基苯基乙烯基硅树脂, 并利用FTIR, ¹H NMR和热重分析(TGA)对产物进行了表征. 将所得甲基苯基乙烯基硅树脂与甲基苯基含氢硅油按一定配比, 在铂络合物催化下硫化成型, 制成发光二极管(LED)封装A/B胶, 用于LED封装. 所得LED封装硅树脂固化后在可见光范围内具有非常高的透光率. 对LED的封装结构进行优化, 获得的LED具有高光效、 高光通量、 窄显色指数和高色温一致性等优点, 可满足功率型LED封装要求.     

Thermoplastic Elastomers Based on Ethylene-vinyl Acetate Copolymer and Waste Nitrile Butadiene Rubber Powder Blends Compatibilized by Chlorinated Polyethylene

Thermoplastic elastomers (TPEs) based on ethylene-vinyl acetate (EVA)/waste nitrile butadiene rubber powder (WNBRP) blends compatibilized by chlorinated polyethylene (CPE) were prepared by melt-compounding. The tensile strength and the elongation at break of the EVA/CPE/WNBRP blends were increased significantly compared with those of the EVA/WNBRP blends. The fracture surfaces of the EVA/CPE/WNBRP blends were smooth; moreover, the WNBRP in the etched EVA/CPE/WNBRP blends were inserted in the EVA matrix tightly. DMA results revealed that when the CPE dosage was 5 phr in the EVA/CPE/WNBRP blend, the Payne effect was weakened significantly.     

Characteristics and Kinetics of Thermal Degradation of Fluoroether Rubber

An advanced, heat-resistant fluoroether rubber (FM-20) was subjected to dynamic thermogravimetric analysis (TGA) in the air atmosphere. The results suggested that its thermal degradation process can be divided into two parts. As the heating rate increased, the initial decomposition temperature and degradation temperature would move to higher ranges. The apparent activation energy of thermal decomposition, calculated by the Kissinger, Friedman and Flynn-Wall-Ozawa methods were 209, 240, and 211kJ/mol, respectively. Furthermore, the probable thermal degradation mechanism was also analyzed by the Coats-Redfern method. As a result, the most reasonable thermal degradation mechanism of FM-20 was g (α) = α^3/2