Methacryloxyethyl phosphate‐grafted expanded polytetrafluoroethylene membranes for biomedical applications

Expanded polytetrafluoroethylene (ePTFE) membranes were modified by graft copolymerization with methacryloxyethyl phosphate (MOEP) in methanol and 2‐butanone (methyl ethyl ketone (MEK)) at ambient temperature using gamma irradiation. The effect of dose rate (0.46 and 4.6 kGy h^?1), monomer concentration (1–40 %) and solvent were studied and the modified membranes were characterized by weight increase, X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). XPS was used to determine the % degree of surface coverage using the C? F (ePTFE membrane) and the C? C (MOEP graft copolymer) peaks. Grafting yield, as well as surface coverage, were found to increase with increasing monomer concentration and were significantly higher for samples grafted in MEK than in methanol solution. SEM images showed distinctly different surface morphologies for the membranes grafted in methanol (smooth) and MEK (globular), hence indicating phase separation of the homopolymer in MEK. We propose that in our system, the non‐solvent properties of MEK for the homopolymer play a more important role than solvent chain transfer reactions in determining grafting outcomes. Copyright © 2005 Society of Chemical Industry     

Ecological aspects of the manufacture and application of highly pure liquid substances

The action mechanism for aggressive and highly pure media on fluoropolymer constructional elements is assumed to consist of two basic microeffects: destructive changes in the fluoropolymer and contamination of the environment. Our approach to a quantitative estimation of the physicochemical stability is based on logic similar to that of a thermodynamic model of a two‐component system. A fluoropolymer and changes in its microstructure are considered the first component of the system. The second component is composed of liquid media contaminated with fluoroorganic compounds extracted from the fluoropolymer. The proposed methods for delivering aggressive and highly pure fluids to consumers allow the exclusion of pollution from working areas with gaseous products through an exception to a number of intermediate stages of product transport. The discussed principles allow the creation of a modern, highly effective, and safe (with respect to the ecology and raw materials) production of aggressive liquid chemicals for consumers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 906–910, 2002     

Restraining the associations of anthracene fluorophore by chemically linking to poly(methyl methacrylate)

Associations (dimer or aggregate) of anthracene (An) fluorophores tend to interrupt the monomer emission and reduce the quantum yield (Φ_PL); therefore, poly(methyl methacrylate) (PMMA) chain was used in this study to chemically link to anthracene and to block the mutual associations among the anthracene fluorophores. With this aim, the target polymers were prepared by anionic polymerizations with 9,10‐dibromoanthracene/s‐butyllithium as initiating system to proceed polymerizations of methyl methacrylate (MMA) directly or in the presence of 1,1‐diphenylethylene (DPE). Use of DPE before addition of MMA produces stable initiating anionic species and avoids potential side reactions during polymerization; however, it also introduces four β‐phenylene rings around the central anthracene ring, which interfere with the corresponding emission pattern and reduce the Φ_PL (32%) value due to potential interactions between phenylene rings and anthracene. On the contrast, polymerization without participation of DPE results in polymer with central anthracene ring directly connected to two PMMA chains, which gives clean vibronic emission pattern with limited association emissions and enhanced Φ_PL (52%) value. Physical blending of anthracene by PMMA is less efficient to restrain the associations and results in a film of lower Φ_PL (20%). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Heat capacities of polyethylene and linear fluoropolymers

Heat capacities at constant pressure, C_p, and at constant volume C_v, were calculated with the help of normal mode frequency spectra and compared to experimental data for crystalline or semicrystalline polyethylene, poly(vinyl fluoride), poly(vinylidene fluoride), polytrifluooroethylene and poly(tetrafluoroethylene). A calculation scheme using a Tarasov function for 2N skeletal vibrational modes and an approximation of the residual 7N normal modes from known data on polyethylene and polytetrafluoroethylene is developed for all homologous, linear fluoropolymers. N is the number of carbon backbone atoms of the repeating unit. Calculations can be carried out over the whole temperature range 0 K to melting. For the two theta temperatures and the constant A₀ used for C_v to C_p conversion, fluorine-concentration dependent curves are given. The relations are expected to hold also for copolymers and blends of intermediate fluorine contents. Recommended experimental (data bank) heat capacities agree to ±2.5% with the calculations.     

Surface properties of fluorinated hybrid coatings

A commercial perfluoropolyether containing alkoxysilane functionalities was employed to prepare organic–inorganic hybrid coatings by using the sol‐gel process in the presence of tetraethoxysilane. Contact angle analysis revealed a strong hydrophobic and oleophobic character of the coatings almost independently from the molecular weight of the starting fluorinated oligomer. Surface tension values were in the range of 14–16 mN/m, suggesting a preferential segregation of fluorinated segments onto the surface of the coating. Atomic force microscopy showed the presence very smooth surfaces permitting to neglect the contribution of the surface roughness to wettability. Friction coefficient values were markedly lower with respect to the value of uncoated glass substrate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1483–1488, 2006     

Adhesion property of novel polyimides with 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride

Novel polyimides were synthesized from 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride (6FPPMDA) by a conventional two‐step process: the preparation of poly(amic acid) followed by solution imidization via refluxing in p‐chlorophenol. The diamines used for polyimide synthesis included bis(3‐aminophenyl)‐3,5‐bis(trifluoromethyl)phenyl phosphine oxide, bis(3‐aminophenyl)‐4‐trifluoromethylphenyl phosphine oxide, and bis(3‐aminophenyl)phenyl phosphine oxide. The synthesized polyimides were designed to have a molecular weight of 20,000 g/mol by off‐stoichiometry and were characterized by Fourier transform infrared, NMR, differential scanning calorimetry, and thermogravimetric analysis. In addition, their intrinsic viscosity, solubility, water absorption, and coefficient of thermal expansion (CTE) were also measured. The adhesion properties of the polyimides were evaluated via a T‐peel test with bare and silane/Cr‐coated Cu foils, and the failure surfaces were investigated with scanning electron microscopy. The 6FPPMDA‐based polyimides exhibited high glass‐transition temperatures (280–299°C), good thermal stability (>530°C in air), low water absorption (1.46–2.16 wt %), and fairly low CTEs (32–40 ppm/°C), in addition to good adhesion properties (83–88 g/mm) with silane/Cr‐coated Cu foils. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1801–1809, 2005     

Melt‐spinning process of a tetrafluoroethylene– hexafluoropropylene copolymer

An industrial melt‐spinning process of tetrafluoroethylene– hexafluoropropylene copolymer (FEP) using an extruder was studied. The novel “spinneret,” having both a large‐diameter spinning nozzle and a high‐temperature vessel, was used to solve the problem of filament breakage on the spinning line caused by high melting viscosity of FEP. The extruder, with its long feed zone, was newly designed to function with a geared pump. The strength of fibers increased with drawing of as‐spun fiber. FEP fibers up to six denier were continuously produced through long‐run production. According to this new process, FEP fibers can be supplied for textile or industrial application. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2366–2371, 2002     

Fluorinated acrylic polymers: Surface properties and XPS investigations

A series of polymers based on methylmethacrylate, butylacrylate, and ω‐perfluorooctylalkylacrylate were prepared by radical polymerization. By changing both the length of the hydrocarbon spacer, between the fluorinated chain and the ester function of the fluorinated monomer, and its concentration, the surface properties of the resulting terpolymers were greatly influenced. Polymers containing small amounts of fluorinated comonomer units had considerably reduced surface energies compared to the copolymer poly (methylmethacrylate‐co‐butylacrylate) taken as reference. The outermost surface composition has been investigated by the XPS technique, confirming the strong fluorine enrichment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 821–827, 2006     

CO2‐assisted polymer processing: A new alternative for intractable polymers

CO₂‐assisted polymer processing is proposed as an alternative route for intractable and high molecular weight polymers based on the plasticization effects of CO₂ and its direct effect on the melting behavior of semicrystalline polymers. A modified processing system was used to process a variety of polymers in the presence of high‐pressure CO₂. The system includes an extruder that was modified to allow for high pressures created by the injection of CO₂. The new design includes a modified feed section that allows a given mass of polymer to interact with CO₂ before and during the extrusion process. The inherent shear mixing and the presence of CO₂ allow for a specific control over the extrudate morphology. Results suggest that this alternative design provides a new and easy route to melt process high melt viscosity polymers of commercial importance, such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), and syndiotactic polystyrene (s‐PS). The increased processability of these systems in CO₂ is related to the plasticization effect of CO₂ that was quantified through a depression in the glass‐transition temperature according to the Chow model. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1501–1511, 2004     

超双疏含氟聚合物的研究进展

超双疏功能性材料在当代化工材料中有着重要的地位,其独特的界面性能使得其在各个领域的应用中大显身手。本文介绍了近年来国内外对含氟聚合物在超双疏领域的研究近况,包括超双疏含氟聚合物的结构特点和合成方法等。含氟聚合物的表面拥有超低的表面能和独特的空间排列方式,通过对比不同结构的含氟聚合物分子与其性能的关系以及对各类含氟聚合物合成方法的调研,发现含氟聚合物作为超双疏涂层材料的使用十分广泛,其结构中含氟单体主要为氟取代丙烯酸酯类,合成方法多为乳液聚合。超疏水含氟聚合物与纳米颗粒材料的结合是当今研究的热点,文中列举了大量研究实例,希望其中的研究方法和合成路线等能对今后该领域的研究起到一定的借鉴作用。