脲醛树脂微胶囊包覆红磷阻燃剂制备工艺的研究 Ⅰ.预聚物合成工艺研究

研究了脲醛树脂的预聚物通过原位聚合对红磷进行包覆的一些影响因素。实验表明影响预聚物质量的主要因素是第一阶段尿醛比(F/U)1,第二阶段尿醛比(F/U)2,反应温度和pH值。制备预聚物的最佳条件为:第一阶段尿醛比为2.3∶1(摩尔比),第二阶段尿醛比为1.3∶1(摩尔比),pH值为5.1,反应温度为75℃。制备的预聚物来包覆红磷,颜色为白色;用微胶囊红磷阻燃聚乙烯,当含量为9%时,在500℃下残余物为4.85%。     

含活性硅氧烷型大分子改性剂BA-MMA-VTES的合成与表征

针对弱极性天然/丁苯橡胶复合体系,从分子设计的角度出发,选择乙烯基三乙氧基硅氧烷(VTES)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)为单体,通过自由基溶液聚合并优化了反应条件:在85℃和115℃分别加入两种不同量的引发剂BPO和DCP,均保温反应2h,合成了三元共聚物BA-MMA-VTES大分子表面改性剂,用于纳米碳化硅、氮化硅陶瓷粉体的表面改性。采用FTIR、NMR、GPC、DSC、TGA等对所合成的三元共聚物的结构、性质和数均相对分子质量进行了分析和表征。通过FTIR、NMR测试结果,证实了BA-MMA-VTES三元共聚物的结构;通过GPC测试,证明BA-MMA-VTES三元共聚物的数均相对分子质量控制在3000～10000;DSC显示合成的大分子只有一个Tg,在3.3℃左右,表明它是无规共聚物,柔性适中;TGA显示三元共聚物主要热分解区间在280～500℃,热稳定性良好。     

Poly(butylene terephthalate)/organoclay nanocomposites prepared by in situ interlayer polymerization and its fiber (II)

Intercalated nanocomposites with poly(butylene terephthalate) (PBT) incorporated between the montmorillonite layers were synthesized from dimethyl terephthalate and 1,4-butane diol by using an in situ interlayer polymerization. The PBT nanocomposites were melt-spun at different organoclay contents to produce monofilaments. The samples were characterized by using wide angle X-ray diffraction, electron microscopy, thermal analysis, and tensile testing. The extent of the clay layer in the PBT was confirmed by using X-ray diffraction and electron microscopy, and the clay layer was found to be highly dispersed on a nanometer scale. The addition of only a small amount of organoclay was enough to improve the thermo-mechanical properties of the PBT hybrid fibers. The hybrids were extruded with various draw ratios (DRs) to examine the tensile mechanical property of the fibers. At DR=1, the ultimate tensile strength of the hybrid fibers increased with the addition of clay up to a critical content and then decreased. However, the initial modulus monotonically increased with increasing amount of organoclay in the PBT matrix. When the DR was increased from 1 to 6, for example, the strength and the initial modulus values of the hybrids containing 3 wt% organoclay decreased linearly.     

Reversible addition fragmentation transfer (RAFT) polymerization of styrene in a miniemulsion: A mechanistic investigation

The RAFT polymerization of styrene in miniemulsion using 1-phenylethyl phenyl-dithioacetate (PEPDTA) as a RAFT agent was investigated, in attempt to reveal the mechanism for the often observed inferior performance such as low polymerization rate, broad molecular weight distribution and particle size distribution in the RAFT miniemulsion polymerization with regular levels of surfactant and co-stabilizer (1 wt% sodium dodecyl sulfate and 2 wt% hexadecane). It is strongly evident that a few of large oligomer particles consisting of oligomer, RAFT agent (RAFT agent refers to the original RAFT agent), and monomer would be formed in the early stage of the polymerization due to the superswelling of the first nucleated droplets. With the regular levels of surfactant and co-stabilizer, the observed low polymerization rate, broadened molecular weight distribution, slow conversion of the RAFT agent, lower N_p, and broadened particle size distribution could be well explained by the formation of these large oligomer particles and their prolonged existence. When the formation of the oligomer particles was suppressed by increasing surfactant and co-stabilizer levels and wise selection of types of RAFT agent, the molecular weight distribution could be narrowed to around 1.3 and particle size distribution could be close to that of the conventional non-living miniemulsion polymerization.     

Viscosity of bulk free radical polymerizing systems under near-isothermal and non-isothermal conditions

A viscometer-reactor assembly is used to generate data on the viscosity, η(t), of an example polymerizing system exhibiting the Trommsdorff effect, namely, the bulk free radical polymerization of methyl methacrylate (MMA), at different temperature conditions [near-isothermal and non-isothermal (near-step increase and near-step decrease in temperature)] and at two different initiator, 2,2′-azoisobutyronitrile (AIBN), concentrations. Two types of cup and bob assemblies, viz., the Haake^® SV-2 and the Haake^® HV-DIN, have been used to measure η(t) of the reaction mass, until reasonably high values of viscosity, well into the gel effect region. Only three sets of experimental data on x_m(t), M_w(t) and η(t) under near-isothermal conditions, are used to develop general correlations for the viscosity. These tuned correlations predict the values of the viscosity for a whole variety of other experimental conditions, including non-isothermal cases, reflecting that the physics of the system is well represented by them. Hence, these correlations can be used for other systems after tuning their parameters. The feasibility of on-line soft sensing is demonstrated for a few cases.     

DQ型高效催化剂在环管PP装置上的应用

介绍了使用DQ型球形高效催化剂在上海石油化工股份有限公司塑料事业部70kt/a环管连续法工业聚丙烯生产装置上应用研究的结果，并对结果进行了讨论。     

Electrosyntheses and characterization of poly(5‐bromoindole) in boron trifluoride diethyl etherate

Poly(5‐bromoindole) (PBrI) films were synthesized electrochemically by direct oxidation of 5‐bromoindole in pure boron trifluoride diethyl etherate. The oxidation potential of 5‐bromoindole in this medium was measured to be only 0.97 V vs. saturated calomel electrode, which was lower than that determined in acetonitrile + 0.1 mol L^?1 Bu₄NBF₄ (1.08 V). PBrI films obtained from this medium showed good electrochemical behavior and good thermal stability. Structural studies showed that the polymerization of 5‐bromoindole ring occurred at 2,3 position. As‐formed PBrI films were thoroughly soluble in strong polar solvent dimethylsulfoxide and partly soluble in tetrahydrofuran. Fluorescent spectral studies indicated that PBrI was a good blue‐light emitter. The excitation and emission spectra of PBrI showed a significant shift to longer wavelength compared with that of the monomer, consistent with the greater extent of electron delocalization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 539–547, 2006     

Curing of mixtures of epoxy resins and 4‐methyl‐1,3‐dioxolan‐2‐one with several initiators

Diglycidyl ether of bisphenol A or 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate were mixed with different proportions of 4‐methyl‐1,3‐dioxolan‐2‐one and cured using lanthanide triflates as initiators. In order to compare the materials obtained, conventional initiators such as boron trifluoride complexes and N,N‐dimethylaminopyridine were also tested. The curing process was followed by differential scanning calorimetry (DSC) and Fourier transform IR in attenuated total reflectance mode. This technique proved that the carbonate accelerates the curing process because it helps to form the active initiating species, although it was not chemically incorporated into the network and remained entrapped in the material. The DSC kinetic study was also reported. © 2006 Wiley Periodicals Inc. J Appl Polym Sci 102: 2086–2093, 2006     

Unipol气相法聚烯烃液体催化剂技术进展

介绍了Unipol气相法聚烯烃工艺液体催化剂的成分、加入反应器的方式和喷嘴结构及控制催化剂液滴尺寸方法等方面的最新进展情况。     

悬浮法合成聚丙烯腈高吸水性树脂

以偶氮二异丁腈为引发剂，用悬浮聚合法合成了交联聚丙烯腈，然后对其进行水解，得到了高吸水性聚丙烯腈。交联剂用量和水解条件对树脂吸水倍数的影响很大。树脂吸去离子水倍数为420倍，平均粒径为250μm。