Rapid identification of trimethyl and triethyl amines using sulphonic acidic ionic liquids: A time-of-flight secondary ion mass spectrometry study of fragmentation reactions

The time-of-flight secondary ion mass spectrometry (TOF-SIMS) has emerged as a powerful tool for the unswerving detection of biomolecules, in particular, proteins and peptides. To date, there is very little information available on the direct determination of trimethyl/triethyl amines using TOF-SIMS. One major hurdle in this regard is an ultrahigh vacuum system, usually needed in TOF-SIMS, which hampers its usability to trimethyl/triethyl amines owing to their high evaporation rate. We designed an efficient and sensitive protocol for rapid identification and sensitive determination of tertiaryalkyl amines using TOF-SIMS. The amines were derivatized by reaction with 1,4-butane sultone and sulphuric acid sequentially to afford the corresponding sulphonic acidic ionic liquids (ILs). The TOF-SIMS analysis of these task-specific ILs (TSILs) was carried out in both positive and negative polarity. The positive ion mass spectra of TSILs showed sharp fragmented peaks for tertiaryalkyl amines at typical level and up to 10 ppm. The possible mechanism for different fragmentation pathways in positive polarity was discussed.     

Reversible fixation and release of carbon dioxide with a binary system consisting of polyethylene glycol and polystyrene‐bearing cyclic amidine pendant group

In this study, we investigated the CO₂‐capture/release behavior of the polystyrene‐bearing cyclic amidine pendant groups, which was synthesized via free radical polymerization of HCl salt of the corresponding styrene monomer followed by neutralization. For comparison, we also prepared the polystyrene bearing N‐formyl‐1,3‐propanediamine pendant groups through the hydrolysis of the cyclic amidine group by treatment with an alkaline solution. First, we examined the CO₂‐capture/release behaviors of the amidine and amine monomers in aqueous solution in terms of conductivity. The conductivity of a wet DMSO solution of the amidine monomer increased upon CO₂ bubbling at 25 °C and reached a stationary value of about 11 mS/m, which indicated the formation of the bicarbonate salt. Conversely, the conductivity decreased to its original value upon N₂ bubbling at 50 °C, reflecting the complete release of the trapped CO₂ molecules. Both solutions showed the changes in the conductivity with quick responses, and no appreciable difference was observed between them. We then investigated the CO₂‐capture/release behaviors of the amidine and amine polymers, by taking advantage of the binary system with polyethylene glycol, and found that the binary system with the amidine polymer captured and released CO₂ more efficiently than that with the amine polymer. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2025–2031     

Morphological,thermal, and biodegradation properties of LLDPE/treated date palm waste composite buried in a soil environment

In this study, date palm waste that was naturally treated as a filler in a linear-low density polyethylene (LLDPE) matrix was recycled to prepare green composites. Two types of LLDPE, based on basic additives, were used. UV stabilizer and the slip and anti-block were added as basic additives. The objective of this study was to examine the effect of these basic additives and the treated filler on the biodegradation, morphological, and thermal properties of the prepared samples by a soil burial test. The samples were characterized by Fourier-transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD). Weight loss was calculated to investigate the biodegradation of the sample, and SEM and thermogravimetric analyses were performed to reveal the morphology and thermal properties before and after burial, respectively. Results showed that the presence of the bio-filler accelerated the biodegradation of the composites. The UV stabilizer had a positive impact on biodegradation factors whereas anti-block additives appeared resistant to biodegradable factors. The morphology and thermal stability of all the prepared samples changed after burial due to the effects of biodegradation during the burial.     

Antibacterial Effects of Silver Doped Polyethyleneglycol Based Polyamidoamine Side Chain Dendritic Polyurethane

Antibacterial activity was imparted with polyamidoamine (PAMAM) side chain dendritic polyurethane (SCDPU‐PEG) by doping of silver particles. Antibacterial activities of both the polyurethane (SCDPU‐PEG) and its silver doped structures were investigated against Escherichia coli bacteria. The silver doped polymeric structures were found to exhibit antibacterial activity while the polymer without silver loading showed no antibacterial activity. Formation of silver doped side chain dendritic polymers was investigated from the UV‐vis plasmon absorption band of silver particles.     

Clickable polyurethanes based on s‐triazine ring containing aromatic diisocyanate bearing pendent alkyne group: Synthesis and postmodification

A new s‐triazine ring containing aromatic diisocyanate bearing a pendent alkyne group, namely, 2,4‐bis(4‐isocyanatophenoxy)?6‐(prop‐2‐yn‐1‐yloxy)?1,3,5‐triazine was synthesized and reacted with various diols viz., 1,10‐decanediol, tetraethylene glycol and polyethylene glycols in the presence of dibutyltin dilaurate as the catalyst to obtain a series of linear polyurethanes. The selected polyurethanes possessing pendent alkyne groups were postmodified with chemically diverse azides viz., 1‐(azidomethyl)benzene, 1‐(azidomethyl)pyrene, and methoxy end‐caped poly(ethylene glycol) azide via copper‐catalysed azide‐alkyne Huisgen 1,3‐dipolar cycloaddition. FTIR and ¹H NMR spectra indicated quantitative click reaction. UV–vis and fluorescence spectroscopic analysis confirmed complete incorporation of pyrenyl groups indicating the formation of fluorescence active polyurethane by postmodification with 1‐(azidomethyl)pyrene. TG analysis of polyurethanes indicated two stage weight loss and their thermal stability, as judged by T ₁₀ values, was governed by weight percent of urethane linkages. The water contact angle measurements revealed improved wettability with increased content of PEG either in the backbone of polyurethanes or as grafted chains. DLS and TEM studies confirmed that certain polyurethanes possessing PEG segments displayed self‐assembly in aqueous solution, which was further supported by pyrene encapsulation studies using UV–vis spectroscopy. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1008–1020     

过载作用下聚乙烯疲劳裂纹扩展行为研究

论文针对中密度聚乙烯材料(MDPE)，采用平板试样进行了I型疲劳裂纹扩展和单次过载下裂纹扩展试验．发现与金属材料类似，单次拉伸过载对聚乙烯(PE)的疲劳裂纹扩展有明显的迟滞作用，降低了裂纹扩展速率．试验还通过变载荷刻线法获取疲劳裂纹扩展前缘的实际形貌和变化规律，对常规变载荷刻线方法进行了调整和验证，其修正方法对高分子材料的疲劳裂纹扩展前缘刻线具有较好的效果．通过观察发现含楔形塑性区的裂尖钝化是裂纹迟滞的主要原因．过载引入的塑性区内残余应力对裂纹迟滞也起了重要作用．论文利用Dugdale模型计算了塑性区尺寸，使用基于残余应力的Wheeler模型对过载迟滞进行了很好的拟合．     

Piezoelectric property improvement of polyethylene ferroelectrets using postprocessing thermal‐pressure treatment

In this work, biaxially stretched polymer foams with well‐defined cellular structures were prepared from polyethylene via blown‐film extrusion and subjected to corona charging to produce a piezoelectric response. The charging parameters were first optimized in terms of charging voltage and needle distance, as well as the gas type and pressure to investigate their effect on the piezoelectric coefficient (d₃₃). The results show that samples charged under nitrogen (N₂) at 100 kPa had better d₃₃ coefficient than those charged under ambient air or N₂ at 20 kPa. Moreover, 2 different thermal pressure treatments were imposed to obtain an optimized eye‐like cellular structure with different cell aspect ratios (AR). The results showed that when the cells were elongated in both the longitudinal and transverse directions (higher AR), higher d₃₃ coefficients were achieved. From all the samples produced, the best results were obtained for a longitudinal aspect ratio (AR‐L) of 7.1, a transversal aspect ratio (AR‐T) of 4.6, and a relative foam density of 0.52 leading to a d₃₃ coefficient of 935 pC/N. This coefficient was further increased using reverse charging and multilayered films, reaching a maximum of 2550 pC/N. This value is much higher than typical ones reported so far for any polyethylene and polypropylene ferroelectrets. These results could increase the use of polyethylene in piezoelectric applications as these materials are very attractive for the large‐scale production of electret‐based sensors and transducers due to their low cost and easy processing.     

导热增强聚乙二醇相变复合材料的制备及其性能

本文以聚乙二醇(PEG)为相变材料,通过添加不同的无机填料,采用熔融共混浇筑方式制备了导热增强型相变复合材料。 通过扫描电子显微镜(SEM)、热常数分析仪、差示扫描量热仪(DSC)、红外热成像和热重分析仪研究了所制备复合材料的微观结构、导热性能与相变过程。 研究结果表明,相比于碳酸钙和氧化铝,在相同添加含量下,氮化硼(BN)可有效提高PEG的导热系数,当BN质量分数为40%时,导热系数可达到3.40 W/(m·K);当填料添加量相同时,片状BN和不规则纳米碳酸钙(CaCO₃)比球形氧化铝(Al₂O₃)对PEG具有更加优良的定型效果,在相变过程中,能够更加有效阻隔PEG的流动,保持复合材料的形状稳定性。     

UHMWPE纤维的超临界CO_2辅助渗透预处理研究

利用Minitab软件设计实验,以超高分子量聚乙烯纤维(UHMWPE)为原料,研究了在不同的超临界CO_2流体状态下,处理压力、温度和时间等因素对三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)渗入率的影响,确定了最佳因素设置范围;通过单因子实验优化了超临界CO_2处理工艺,并对经过电子束辐照的UHMWPE纤维凝胶含量和蠕变率进行了测试。研究结果表明:处理温度对TMPTMA的渗入率影响最大,其次为压力,时间的影响最小,确定了最优工艺条件为处理压力25MPa,温度80℃,时间30min;TMPTMA渗入率越高,电子束辐照后UHMWPE纤维的增感辐照交联效应和抗蠕变效果越好。     

Structural transformation from shish‐kebab crystals to micro‐fibrils through hot stretching process of gel‐spun ultra‐high molecular weight polyethylene fibers with high concentration solution

Structural evolution of gel‐spun ultra‐high molecular weight polyethylene fibers with high concentration solution via hot stretching process was investigated by in situ small‐angle X‐ray scattering, in situ wide‐angle X‐ray diffraction measurements, scanning electron microscopy, and differential scanning calorimetry. With the increase of stretching strain, the long period continuously increases at relative lower stretching temperature, while it first increases and then decreases rapidly at relative higher stretching temperature. The kebab thickness almost keeps constant during the whole hot‐stretching process and the kebab diameter continually decreases for all stretching temperatures. Moreover, the length of shish decreases slightly and the shish quantity increases although there is almost no change in the diameter of shish crystals during the hot stretching process. The degree of crystal orientation at different temperatures is as high as above 0.9 during the whole stretching process. These results indicate that the shish‐kebab crystals in ultra‐high molecular weight polyethylene fibers can transform continuously into the micro‐fibril structure composed mostly of shish crystals through the hot stretching process. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 225–238