Chemoselective Polymerization Control: From Mixed‐Monomer Feedstock to Copolymers

A novel chemoselective polymerization control yields predictable (co)polymer compositions from a mixture of monomers. Using a dizinc catalyst and a mixture of caprolactone, cyclohexene oxide, and carbon dioxide enables the selective preparation of either polyesters or polycarbonates or copoly(ester‐carbonates). The selectivity depends on the nature of the zinc–oxygen functionality at the growing polymer chain end, and can be controlled by the addition of exogeneous switch reagents.     

Synergism of polysiloxane and zinc borate flame retardant polycarbonate

Liquid polysiloxane (PSI) and zinc borate (ZB) were combined for the flame retardance of polycarbonate (PC). During polymer combustion, for the PC flame-retarded with PSI only, PSI can form char residue containing silica on the material surface. But the liquid silicone tends to drip with melting polymer and volatilize in high temperature, thus decreasing the charring performance. In the case of only ZB flame retardant involved, this inorganic flame retardant and possible some of its decomposition products (B₂O₃) more difficultly move to the surface and it appears that they do not effectively contribute to the char formation. Present study suggests that the existing synergism between PSI and ZB is the result of chemical reaction via forming cross-linking B–O–Si structure. As results, the loss of Si/silicone is reduced by eliminating the melt dripping. Meanwhile, boron species can be “dragged” by PSI (in the form of borosiloxane) to the surface of the char residue. Consequently, Si and B elements together contribute to the integrity of char residue layer with better quality, achieving obviously improved flame retardance compared with only PSI and only ZB flame retardant systems.     

具有高散射能力的聚碳酸酯复合材料的制备与性能研究

以双酚A型聚碳酸酯(PC)为基体、苯乙烯-丙烯腈共聚物(SAN)为散射体,通过熔融共混方法制备了同时具备高透光率和高雾度的高散射聚碳酸酯光散射片,研究了SAN含量对光散射片微观结构和光散射性能的影响,发现透光率和雾度同时随着散射体含量增加而提高的现象.研究结果表明,当SAN含量低于30%时,分散相为球形颗粒,颗粒的平均粒径随着SAN含量的增加而增加,而颗粒的数量浓度则随之减小,这使得其透光率和雾度均随着SAN含量的增加而增加,当SAN含量为30%时,透光率和雾度达到最大值,分别为89.1%和91.7%.并结合Mie散射理论解释说明了透光率和雾度同时随着散射体含量的增加而提高的现象.但当SAN含量的进一步增加,分散相颗粒尺寸已远大于光波的波长,不再适用于Mie散射理论,且部分不再呈球形颗粒,使得PC片的透光率和雾度略有降低.     

Toughening of polycarbonate through reactive melt blending: Effect of hydroxyl content and viscosity of hydroxyl-terminated polydimethysiloxane

In this study, four hydroxyl-terminated polydimethylsiloxanes(PDMSOH) with different viscosities and hydroxyl contents were used to improve the toughness of polycarbonate(PC) through reactive melt blending. A largely improved toughness of PC has been achieved, and the low temperature toughness of PC/PDMSOH blends could overtake that of PC homopolymer in much higher temperatures(e.g.-10 °C versus 23 °C). Moreover, it was found that the more the hydroxyl content, the less the PDMSOH was needed to reach the highest toughness, suggesting that equivalent molar ratio between the carbonyl group content of PC and the hydroxyl group content of PDMSOH was required for the toughening of PC. Ultraviolet spectrophotometry was used to analyze the possible reaction between PC and PDMSOH. Contact angle was measured to assess the change of interfacial interaction between PC and PDMSOH as change of viscosity and hydroxyl content. The formation of PC-co-PDMSOH copolymer was believed to be the key for the toughening effect. This work gives a profound recommendation of the optimum kind and dosage of PDMSOH which should be used to improve the toughness of PC and will find immediate industrial applications.     

Polycarbonate nanoparticles spray coated on silicon substrate using micro-electromechanical-systems-based high-frequency ultrasonic nozzle

Mono-disperse polycarbonate (PC) nanoparticles 20 nm in diameter was spray coated on silicon substrate using a novel high-frequency ultrasonic nozzle. Specifically, Bisphenol-A polycarbonate with a molecular weight (M_w) of approximately 6.4 × 10⁴ g/mol was first dissolved in pyridine. The resulting solution was sprayed into surfactant-containing de-ionized (DI) water using a 300 kHz silicon-based multiple-Fourier horn nozzle (MFHN). As pyridine was extracted into the water, PC nanoparticles formed but remained dispersed. This suspension of PC nanoparticles was then sprayed onto a silicon substrate using a 500 kHz 3-Fourier horn nozzle. Scanning electron microscopy (SEM) of the dried substrate revealed that PC nanoparticles were spread uniformly with no aggregation.     

Study of Glow Wire Ignition Temperature (GWIT) and Comparative Tracking Index (CTI) performances of engineering thermoplastics and correlation with material properties

Recent regulation IEC 60335-1 ed.4 (2008) was introduced for materials used in electric appliance, establishing new limits in Glow Wire Ignition Temperature (GWIT) performance for materials used for electric connectors. Development of new products with high GWIT is possible, but the main issue is to keep good mechanical properties and processability, as well as tracking resistance (Comparative Tracking Index-CTI). Only a few patents and scientific publications exist about glow wire test performance of polymers. In this work we report GWIT and CTI properties for three engineering thermoplastic polymers (PBT, PET and PC). We have also studied the phenomena involved in this test, treating the phenomena with the parameterisation approach already used in the studies of the fire behaviour of polymers. PC, PBT and PET filled with 30% w/w glass fibres have been tested, and material properties that can be related to GWIT and CTI performance have been measured by TGA, Laser Flash Thermal Diffusivity (LFTD), Pyrolysis-GC/MS. CTI seems to be correlated with the char formation tendency of the materials, so PBT show a higher tracking resistance than PET and PC. Polycarbonate was the only material that passed the glow wire test (GWIT higher than 775 °C) but generally GWIT performance is not directly related with degradation temperature, since PET is thermally more stable compared with PBT, but less stable in glow wire test. The ignition process, together with the unsteady heat and mass transfer process characteristic of glow wire testing, are affected by many parameters at the same time. That’s why it is not easy to relate results of TGA, Laser flash, Pyrolysis-GC/MS with the glow wire ignition temperature of the materials tested, but the whole of these properties can give useful indication.     

Plasma Treatment of Polymers

Abstract

Plasma treatment of polymers encompasses a variety of plasma technologies and polymeric materials for a wide range of applications and dates back to at least the 1960s. In this article we provide a brief review of the United States patent literature on plasma surface modification technologies and a brief review of the scientific literature on investigations of the effects of plasma treatment, the nature of the plasma environment, and the mechanisms that drive the plasma–surface interaction. We then discuss low‐radio‐frequency capacitively coupled nitrogen plasmas and their characteristics, suggesting that they provide significant plasma densities and populations of reactive species for effective plasma treatments on a variety of materials, particularly when placing the sample surface in the cathode sheath region. We further discuss surface chemical characterization of treated polymers, including some results on polyesters treated in capacitively coupled nitrogen plasmas driven at 40 kHz. Finally, we connect plasma characterization with surface chemical analysis by applying a surface sites model to nitrogen uptake of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) treated in a 40 kHz nitrogen plasma. This example serves to suggest an interesting practical approach to comparisons of plasma treatments. In addition, it suggests an approach to defining the investigations required to conclusively identify the underlying treatment mechanisms.     

聚碳酸酯聚氨酯弹性体的模拟生物老化性能的研究

研究了聚碳酸酯聚氨酯的水解剂，氧化，钙化等生物老化性能，并与聚醚聚氨酯样品做了比较，结果表明，胺扩链样品具有较好的耐水解性能，聚碳酸酯氨酯的抗氧化性能优于聚醚聚氨酯，同了聚醚氨酯一样，聚碳酸酯聚氨酯同样受钙的影响，含水氯化钙对聚碳酸酯聚氨酯的相结构产生影响，并对弹性具有增强作用。     

Completely Recyclable Monomers and Polycarbonate: Approach to Sustainable Polymers

It is of great significance to depolymerize used or waste polymers to recover the starting monomers suitable for repolymerization reactions that reform recycled materials no different from the virgin polymer. Herein, we report a novel recyclable plastic: degradable polycarbonate synthesized by dinuclear chromium‐complex‐mediated copolymerization of CO₂ with 1‐benzyloxycarbonyl‐3,4‐epoxy pyrrolidine, a meso ‐epoxide. Notably, the novel polycarbonate with more than 99 % carbonate linkages could be recycled back into the epoxide monomer in quantitative yield under mild reaction conditions. Remarkably, the copolymerization/depolymerization processes can be achieved by the ON/OFF reversible temperature switch, and recycled several times without any change in the epoxide monomer and copolymer. These characteristics accord well with the concept of perfectly sustainable polymers.     

The effect of impurities on the viscoelastic response of polycarbonate reinforced with short glass fibers

Observations are reported in oscillatory torsion tests at room temperature on unfilled and fiber-reinforced polycarbonates melt-blended with impurities (acronitrile–butadiene–styrene, high-impact polystyrene, low-density polyethylene, poly(ethylene terephthalate) and Nylon 6,6). Constitutive equations are derived for the viscoelastic behavior of glassy polymers. With reference to the theory of cooperative relaxation, a polymer is treated as an ensemble of meso-regions with arbitrary shapes and sizes. The time-dependent response of the ensemble is attributed to rearrangement of meso-domains. The rearrangement events occur at random times, when meso-regions are excited by thermal fluctuations. Stress–strain relations are derived by using the laws of thermodynamics. The governing equations are determined by four adjustable parameters that are found by fitting the experimental data. Fair agreement is demonstrated between the observations and the results of numerical simulation. The study focuses on the effects of the concentration of impurities and glass fibers on material parameters.