高抗冲聚苯乙烯的研制 Ⅰ.预聚合反应动力学及相转变过程的研究

对HIPS预聚合反应阶段的动力学及相转变行为进行了研究,发现基础胶的种类、用量、搅拌速率及阻聚剂含量对苯乙烯预聚合反应动力学和相转变过程均有不同程度的影响。     

废聚苯乙烯制备丙烯酸改性醇酸树脂

通过采用引发剂（BPO）使废聚苯乙烯和丙烯酸及其单体共聚接枝，增加其反应性基团，然后与蓖麻油酸、甘油、苯酐合成丙烯酸改性醇酸树脂，该树脂具有成本低、综合性能好等特点。介绍了该树脂的生产工艺、性能指标及其主要影响因素。     

Scaling laws and polystyrene networks: a quasi-elastic light scattering study

Randomly crosslinked networks with a range of crosslink densities were prepared by γ-irradiation. Quasielastic light scattering measurements were made on the gels swollen to equilibrium in cyclohexane at 308, 318 and 333 K. The longitudinal osmotic modulus M_os was obtained from the intensity of the dynamically scattered light, and the cooperative diffusion coefficient D_c calculated from the relaxation rate of the autocorrelation function. The concentration dependence of these parameters at the theta temperature was found to be consistent with the scaling predictions, but at higher temperatures where excluded volume conditions prevail, deviations from scaling behaviour were observed. These discrepancies are probably caused by defects in the network structure.     

Intercalated PS/Na+‐MMT Nanocomposites Prepared by Ultrasonically Initiated In Situ Emulsion Polymerization

Summary: A new technique, ultrasonically initiated in situ emulsion polymerization, was employed to prepare intercalated polystyrene/Na⁺‐MMT nanocomposites. FTIR, XRD, and TEM results confirm that the hydrophobic PS can easily intercalate into the galleries of hydrophilic montmorillonite via ultrasonically initiated in situ emulsion polymerization, taking advantages of the multi‐effects of ultrasonic irradiation, such as dispersion, pulverization, activation, and initiation. Properly reducing SDS concentration is beneficial to widen the d‐spacing between clay layers. However, the Na⁺‐MMT amount has little effect on the d‐spacing of nanocomposites. The glass transition temperature of nanocomposites increased as the percentage of clay increased, although the average molecular weight of PS decreased, and the decomposition temperature of the 1obtained nanocomposites moves to higher temperature.

TEM of PS/Na⁺‐MMT nanocomposite prepared by ultrasonically initiated in situ emulsion polymerization.     

Wetting properties of polystyrene ionomers treated with plasma source ion implantation

The wetting properties of polystyrene‐based ionomers treated with plasma source ion implantation (PSII) were investigated by the measurement of water contact angles. When sulfonated ionomers were aged for a few days, the hydrophobic recovery for the ionomers became much slower than that for the nonionic polymers. However, when the samples were aged over 20 days, the water contact angle of the ionomers converged with that of the nonionic polymer. Thus, it was concluded that the ionic interaction between the ionic groups and the presence of ionic groups together resulted in the slow hydrophobic recovery and that the aging effect was significant for the ionomers. For the methacrylate ionomer of low ion content, on the other hand, it was found that the PSII treatment produced only a small change in hydrophobic recovery behavior. Thus, it was suggested that the low ionic content coupled with the small size of the ionic unit might cause changes only of a very insignificant degree in hydrophobic recovery behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2500–2504, 2002     

Preparation,morphology, and mechanical properties of elastomers based on α,ω‐dihydroxy‐polydimethylsiloxane/polystyrene blends

α,ω‐Dihydroxy‐polydimethylsiloxane/polystyrene (PDMS/PS) blends were prepared by the solution polymerization of styrene (St) in the presence of α,ω ‐dihydroxy‐polydimethylsiloxane (PDMS), using toluene as solvent and benzoyl peroxide (BPO) as initiator. The PDMS/PS blends obtained by this method are a series of stable, white gums, which were vulcanized to elastomers at room temperature with methyl‐triethoxysilicane (MTES). The use level of MTES was far more than the necessary amount used to end‐link hydroxy‐terminated chains of PDMS, with the excess being hydrolyzed to crosslinked networks, which were similar to SiO₂ and acted as filler. Investigations were carried out on the elastomeric materials by extraction measurement, swelling measurement, and scanning electron microscopy. The extraction data show that at each composition the amount of soluble fraction is less than expected and the difference between experimental and theoretical values becomes more and more significant as PS content increases. This is mainly due to the grafting of PS onto PDMS and the entanglement of PS in the interpenetrating polymer network (IPN), which consists of either directly linked PDMS chains or chains linked via PS grafts and is formed by free radical crosslinking of PDMS during the radical polymerization of St. PS grafted on PDMS is insoluble and PS entangled in the IPN is difficult to extract. Both render the soluble fraction to be less than expected. As the St content in preparing PDMS/PS blends increases, the probability of grafting PS onto PDMS also increases, which may subsequently produce a higher crosslinking level of PDMS networks that linked via PS grafts by radical crosslinking. As a result, not only the amount of insoluble PS increases but also PS entangled in the IPN is more difficult to extract. Scanning electron microscopy demonstrates that the elastomer system has a microphase‐separated structure and a certain amount of PS remains in the PDMS networks after extraction, which is in accordance with the extraction data. Moreover, the mechanical properties of the elastormeric materials have been studied in detail. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3542–3548, 2004     

Small‐angle X‐ray scattering study of modified porous suspension–poly(vinyl chloride) particles

Small‐angle X‐ray scattering (SAXS) was applied to investigate the microstructure of unmodified and modified porous commercial suspension‐type poly(vinyl chloride) (PVC) particles. The modified PVC particles were prepared by an in situ stabilizer‐free polymerization/crosslinking of particles absorbed with a monomer/crosslinker/peroxide solution. The modifying polymers include styrene with or without divinyl benzene (DVB) as a crosslinker and methyl methacrylate (MMA) with or without ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The SAXS method was used to highlight the effect of polystyrene (PS) on the microstructure of PVC particles and to evaluate the characteristic lengths, both in the PVC/PS and the PVC/XPS (PS crosslinked with 0 and 5% DVB, respectively) systems. A model is suggested, where during the synthesis modification process, swelling of PVC by styrene and styrene polymerization occur simultaneously. PVC swelling by styrene causes destruction of the PVC subprimary particles, whereas styrene polymerization leads to phase separation resulting from incompatibility of the polymers. It was further suggested that because of PVC swelling by styrene, structure of the subprimary particles is lost. Therefore the characteristic lengths of PVC/PS and PVC/XPS, as calculated from the SAXS measurements, were attributed to the size of the phase‐separated PS and XPS inclusions, respectively. The SAXS method also shows that PMMA and XPMMA do not influence the PVC microstructure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1024–1031, 2005     

聚苯乙烯／聚乙烯塑料合金的研究

以氢化SBS(SEBS)为相容剂,对聚苯乙烯/聚乙烯塑料合金进行了研究,着重讨论了体系中组成、相容剂含量、PS分子量以及合金制备条件对合金结构与性能的影响。     

橡胶对HIPS树脂落锤指标的影响

通过对高抗冲聚苯乙烯树脂出现产品落锤指标偏低问题的分析，从橡胶配量及其粒径大小上进行了改进，同时改进了工艺操作，采取了提高反应釜搅拌速度、降低乙苯浓度等措施。结果产品合格率达到９９％以上，优级品率达到９８％以上。     

Crystallization and morphological features of syndiotactic polystyrene induced from glassy state

Spherulitic growth rates and microstructure of syndiotactic polystyrene (sPS) cold-crystallized isothermally at various temperatures, T_c (115–240 °C), have been investigated by small-angle light scattering (SALS), optical microscopy and transmission electron microscopy. The derived activation energy for sPS chain mobility at the crystal growing front is 5.4 kJ/mol, which is relatively lower than that of isotactic polystyrene, 6.5 kJ/mol. In addition, the Hv scattering invariant (Q_Hv) measured by SALS on the crystallized sPS samples displays a pronounced minimum at 150 °C. Despite a wide range of T_c used, however, the sample crystallinity estimated by Fourier transformation infrared spectroscopy remains unchanged. Prior to crystallization, the correlation length derived from the Vv patterns on the basis of Debye–Bueche model is ca. 1.13 μm regardless of T_c used. Interconnected domains with a width of ca. 1.8±0.5 μm are readily observed in all the crystallized samples under phase contrast microscopy and the phase-separated structure is conserved within sPS spherulites whose diameters are increased with increasing T_c.

Based on the above facts, we conclude that the presence of a Q_Hv minimum is ascribed to the resultant events of the two competitive transitions i.e. liquid–solid crystallization, and liquid–liquid demixing resulting from the spinodal decomposition (SD). At lower T_c, the unstable SD transition overwhelms the crystallization. Despite the low chain mobility, the coarsening process driven by the interfacial energies has reached a certain level before crystalline nucleation takes place. At higher T_c, on the other hand, cold crystallization becomes the dominant process due to the enhanced chain mobility, leading to the suppression of ongoing SD coarsening process. At an intermediate T_c range, comparable competition of the phase separation and crystallization prohibits the development of ordered symmetry within spherulites, giving the presence of Q_Hv minimum.