Carboxylic acid functionalization of nylon 6 by radiation grafting and conversion to zinc salts: Effects on physical properties

 Functionalization of polymers by grafting monomeric species on to the backbone of molecular chains with the use of γ-radiation has been used extensively. In this work methacrylic acid was grafted onto a commercial grade of polycaproamide (Nylon 6) by preirradiating the polymer granules to 15 kGy at a rate of 1.0 kGy per hour and subsequently immersing these in a 10% aqueous solution of methacrylic acid in the presence of small quantities of FeSO₄ as homopolymerization inhibitor. The polymer was subsequently neutralized by mixing it with zinc acetylacetonate in a laboratory scale melt mixing device. The acid-grafting polymer modification resulted in an increase in glass transition temperature, while the addition of zinc acetylacetonate gave rise to two transitions: The lower transition corresponds to a miscible mixture of free polyamide and acid-grafted polymer, both plasticized with undecomposed zinc compound, while the upper transition corresponds to the zinc salt of the acid grafted polyamide. Through rheological measurements it was shown that both the acid-grafted polymer and the derived zinc salt have a branched structure, possibly containing also some crosslinked domains. Large improvements in solvent resistance were observed for both type of polymer modifications. Received: 13 December 1996 Accepted: 10 February 1997     

Zusatzeffekt von Tensiden auf die Inkompatibilität zwischen Polymersäuren und nichtionischen Polymeren

Zusammenfassung Das Vorkommen der Ausfällung zwischen Polykarbonsäuren und nichtionischen Polymeren im Wasser wurde durch Zufügung der Tenside (anionisch, kationisch und nichtionisch) beeinflußt. Die Grenzkonzentrationen der Tenside für Auflösung wasserunlöslicher Komplexe von Polymersäuren (Polyakryl- und Polymethakrylsäure) und Polyvinylpyrrolidon (PVP) wurden bestimmt und in Bezug auf die Wechselwirkungen zwischen je zwei Komponenten im ternären System, d. i., Tensid-Polymersäure, Tensid-PVP, und Polymersäure-PVP, erläutert.

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The precipitation formation between polycarboxylic acids and nonionic polymers in water was suppressed by addition of surfactants (anionic, cationic and nonionic). The critical surfactant concentrations needed for dissolving the precipitates were determined about the water-insoluble complexes of polymeric: acids (polyacrylic and polymethacrylic acids) with polyvinylpyrrolidone (PVP). The results were discussed with regard to each two component interaction in the ternary system, i. e., surfactant-polymeric acid, surfactant-PVP, and polymeric acid-PVP.

     

氟化氢与涂有聚合物膜下二氧化硅的反应研究

ＨＦ与ＳｉＯ２的反应是一种亲核取代反应，但高温下此反应不能发生．当涂覆在ＳｉＯ２表面的聚合物膜中含有某些特殊的有机化合物或超强酸时，可以促进该反应的发生，这些化合物被称为诱蚀剂．诱蚀剂分三类：（１）三级胺与ＨＦ形成季铵盐得到浓度很高的氟阴离子使该反应很容易发生；（２）强的偶极非质子官能团化合物与ＨＦ中的氢形成氢键使氟的亲核活性增加，有助于该反应发生；（３）超强酸因其质子对ＳｉＯ２骨架中氧的牢固结合能力活化了反应的离去基团，对ＨＦ与ＳｉＯ２的亲核反应起到催化作用．聚合物膜对添加在其中的小分子诱蚀剂起到阻止逃逸的栅栏作用，而本身带有诱蚀官能团的聚合物可以同时充当成膜物及诱蚀剂的作用．通过光化学反应可以选择性地实现聚合物膜下ＨＦ与ＳｉＯ２的刻蚀反应．     

Complexation of well-controlled low-molecular weight polyelectrolytes with antisense oligonucleotides

The influences of polymer-related properties such as molecular weight, charge density, counter ion, and hydrophilic block on the complexation of polyelectrolytes and a fluorescein-labeled oligonucleotide (ON) were investigated. A series of well-defined and well-controlled 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) polymers and block copolymers were prepared using living anionic and radical polymerization methods. Fluorescence measurement was used to reveal the effects of polymer molecular weight, charge density, and counter ion type on the complexation. PolyDMAEMA samples having double molecular weights of the chosen oligonucleotide gave the optimal complexation performance. Kinetic studies showed that high-molecular weight/high-charge density polymer samples produced very stable complexes. The fully charged polyDMAEMA displayed the strongest binding with the ON. These complexes were therefore less sensitive to the changes in the environment. PolyDMAEMA–DMSQ samples had slightly higher complexation ability than polyDMAEMA–MCQ (DMSQ: dimethylsulfate quat; MCQ: methylchloride quat). Both poly(DMAEMA-b-HEMA) and poly(DMAEMA–MCQ-b-PEG) block copolymers showed good complexation ability and steric stability [HEMA: 2-hydroxyethyl methacrylate; PEG: poly(ethylene glycol)]. PEG, but not HEMA block, enhanced the effectiveness of polyDMAEMA–MCQ binding with the ON.     

Nanostructure evolution studies of bulk polymer materials with synchrotron radiation: progress in method development

The prospects of a modern analysis of nanostructure evolution during the processing of polymer materials by means of scattering from synchrotron radiation are demonstrated in examples. The beam sources have gained stability, shortages are located in beamline setups and in method development for the quantitative analysis of voluminous data sets.By using the proposed multidimensional chord distribution function (CDF) analysis method, nanostructure information from small-angle X-ray scattering (SAXS) data are extracted and visualised. The method can be automated if the beamline setup is able to deliver a full data set with simple constraints. In this case even a simultaneous data evaluation is possible (while one pattern is accumulated, the previous one is analysed). The advantages of the method are demonstrated in a study of the straining of a thermoplastic elastomer. The possibilities of an automated analysis are demonstrated in an investigation of the crystallisation behaviour of high-pressure injection-moulded polyethylene (HPIM-PE). The achievable results of nanostructure analysis of polymer materials are discussed. It is shown that the time-resolved SAXS of polymer materials studied during a transformation and analysed by the CDF method is not just a powerful tool to investigate the relationship between structure and properties of materials; the information that can be gained concerning the processes that control nanostructure evolution is equally important. In the future the enlightenment of such relationships may help to tailor polymer materials with respect to their properties and, beyond that, to improve assessments concerning their aging.     

N—（3—二茂铁乙酰胺基）丙基吡咯聚合物修饰的葡萄糖电极的研究

于铂电极上修饰一层Ｎ－（３－二茂铁乙酰胺基）丙基吡咯聚合物膜，应用循环伏安法对聚合物的电化学性能进行研究，发现了Ｎ－位取代吡咯聚合物的电活性大大降低，聚合物中 二茂铁基团氧化还原性能稳定，制成酶电极后，在＋０．２Ｖ以葡萄糖有一明显的催化峰，而对抗坏血酸，尿酸则几乎没有呼应，该葡萄糖电极性能稳定，连续工作十天，响应值基本不变。     

On-line analysis of polymer melt processes

Molten polymer process streams are difficult to analyze either in- or on-line because of sampling problems due to the high temperature and viscosity of the molten state. Real-time monitoring of chemical compositions in these processes can significantly improve safety and product quality and minimize process costs and waste. The information content of the mid-infrared spectrum combined with the recent development of rugged process Fourier transform (FT) IR spectrometers is stimulating the application of process FT-IR to industrial polymer melt processes. Sampling considerations for polymer melts are reviewed. Also, the use of FT-IR spectrometry for on-line measurements of the polymer composition for polymer blends and copolymers in the melt, and the question of how this information could be used to monitor and control the quality of the product given by the process are discussed.     

The spatial distribution of poly(methyloctylsiloxane) deposited by solvent evaporation in the pores of HPLC silica particles

Summary Poly(methyloctylsiloxane) (PMOS), sorbed into the pores of HPLC silica particles by solvent evaporation, can function as a useful stationary phase for reversed-phase chromatography. The present work addresses the question of how the PMOS is distributed in the pores. Measurements of the surface area (BET, N₂) of a series of partially loaded samples (0–40% PMOS, m/m) using a typical batch of HPLC silica (10 μm irregular particles with 6 nm pores) show that the specific surface area of the samples decreases linearly with the specific loading (mass of PMOS per gram of silica). This result is not consistent with a “film” model in which the PMOS is deposited uniformly on the pore walls, but is consistent with a model in which long segmented “plugs” of PMOS are deposited within the pore system. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

The use of ATR-IR to identify the components separated by paper chromatography

Summary A modified procedure for the identification of separated components in paper chromatography using attenuated total reflection infrared spectroscopy is described. This combined method, though inferior in sensitivity and resolution to the modern separation systems interfaced with sophisticated analytical instruments, is simple, relatively less expensive and suitable for routine analysis of components like polymer additives.