Synthesis and characterization of oxidized cellulose

Samples of oxidized cellulose (OC) with various carboxyl contents and degrees of crystallinity were obtained by the oxidation of native and mercerized cellulose with a solution of nitrogen(IV) oxide in CCl₄. A detailed characterization of these OC samples was performed. The effect of oxidation conditions (concentration of N₂O₄ in the solution and oxidation time) and starting cellulose material on OC characteristics (carboxyl, carbonyl and nitrogen content, degree of crystallinity and polymerization, surface area and swelling, and acidic properties) was investigated. Reactivity in the oxidation process was higher in mercerized cellulose than in native cellulose. The action of dilute solutions (10–15%) of N₂O₄ did not affect the degree of crystallinity of cellulose samples. Under these conditions, the oxidation took place mainly in amorphous regions and on the surface of crystallites. Oxidation in a concentrated (40%) N₂O₄ solution led to the destruction of crystallites, which increased the surface area and swelling of cellulose in water. The surface area and the swelling of OC samples increased with a decrease in the index of crystallinity. The acidic properties of OC were shown to increase with an increase of swelling in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4785–4791, 2004     

Antimicrobial activity on the copolymers of 2,4‐dichlorophenyl methacrylate with methyl methacrylate: Synthesis and characterization

Copolymers of monomers 2,4‐dichlorophenyl methacrylate (2,4‐DMA) and methyl methacrylate (MMA) were synthesized with different monomer feed ratios using toluene as a solvent and 2,2′‐azobisisobutyronitrile (AIBN) as an initiator at 70 °C. The copolymers were characterized by IR‐spectroscopy, and copolymer composition was determined with UV‐spectroscopy. The linearization method of Fineman–Ross was employed to obtain the monomer reactivity ratios. The molecular weights and polydispersity indexes were determined by gel permeation chromatography (GPC). Thermogravimetric analyses of polymers were carried out in nitrogen atmosphere. The homo‐ and copolymers were tested for their antimicrobial properties against selected microorganisms. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5227–5234, 2004     

Synthesis and characterization of alt‐bipyridinylene‐phenylene copolymers containing ruthenium(II) complexes

Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by ¹H and ¹³C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004     

Design and synthesis of Ru(II-bipyridyl-containing conjugated polymers

A series of novel π-conjugated polymers containing ruthenium bipyridine complexes was synthesized by a cross-coupling reaction and characterized. These polymers exhibit absorption maxima around 330–350 nm (π-π*) and 460–500 nm metal-to-ligand charge transfer (MLCT), respectively. They are soluble in common organic solvents, and all polymers can be converted into transparent films. We investigated the influence of different donating and acceptor diethynylarenes of the ultraviolet-visible spectra. The oxidation potential, which was measured by cyclic- and square-wave voltametry, showed a typical Ru^2+/3+ exhibited at 1.25 V versus the saturated calomel electrode. The polymers were further characterized with photoluminescence measurements. When excited at 442 nm ( 11a ), the polymer exhibited an emission peak at 690 nm. This peak was attributed to the MLCT states. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 722–732, 2004     

Dendrimers as scaffolds for multifunctional reversible addition–fragmentation chain transfer agents: Syntheses and polymerization

The synthesis and characterization of novel first‐ and second‐generation true dendritic reversible addition–fragmentation chain transfer (RAFT) agents carrying 6 or 12 pendant 3‐benzylsulfanylthiocarbonylsulfanylpropionic acid RAFT end groups with Z‐group architecture based on 1,1,1‐hydroxyphenyl ethane and trimethylolpropane cores are described in detail. The multifunctional dendritic RAFT agents have been used to prepare star polymers of poly(butyl acrylate) (PBA) and polystyrene (PS) of narrow polydispersities (1.4 < polydispersity index < 1.1 for PBA and 1.5 < polydispersity index < 1.3 for PS) via bulk free‐radical polymerization at 60 °C. The novel dendrimer‐based multifunctional RAFT agents effect an efficient living polymerization process, as evidenced by the linear evolution of the number‐average molecular weight (M_n) with the monomer–polymer conversion, yielding star polymers with molecular weights of up to M_n = 160,000 g mol^?1 for PBA (based on a linear PBA calibration) and up to M_n = 70,000 g mol^?1 for PS (based on a linear PS calibration). A structural change in the chemical nature of the dendritic core (i.e., 1,1,1‐hydroxyphenyl ethane vs trimethylolpropane) has no influence on the observed molecular weight distributions. The star‐shaped structure of the generated polymers has been confirmed through the cleavage of the pendant arms off the core of the star‐shaped polymeric materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5877–5890, 2004     

Understanding the quality concept in health care

During the past three decades there has been an intense debate on the quality of health care. Errors in medicine, practice variations, competence of physicians, scarcity and lack of resources have all been reasons for discussing the quality of care. A clear definition of quality should explain the nature of the debate, improve uniformity of speech and facilitate meaningful actions such as quality assurance or quality improvement. However, in due course many different definitions have been proposed and principles of quality assurance in health care have been frequently questioned, because of their industrial nature. It raises questions on our understanding of quality in health care. In this paper, we (i) explore the nature of the quality concept, (ii) explain its meaning by Wittgenstein's theory on rule-following, and (iii) argue for understanding medical care as a reflexive practice, in order to integrate the meaning of quality in medical care.     

Effect of the particle size distribution on the low shear viscosity of high‐solid‐content latexes

The production of high‐solid‐content, low‐viscosity latexes is an active field in both industry and academia. The viscosity of polymer dispersions has a clear dependence on the particle size distribution (PSD). An example is the rule of thumb that a bimodal PSD enables the reduction of the viscosity with respect to monomodal systems. Despite important progress in theoretical work, not much has been done to quantitatively predict the low shear viscosity of aqueous polymer dispersions as a function of the complex PSD. In this work, the capability of a low‐shear‐viscosity equation to quantitatively account for the influence of both the PSD and the physicochemical characteristics of the dispersions is experimentally assessed. An analysis, consistent with theoretical concepts, of the data with semiempirical correlations is proposed. Next, with values of the parameters of the viscosity equation obtained experimentally, the effect of a latex with a 70% solid content on the low shear viscosity is examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3936–3946, 2004     

Viscoelastic behavior of polypropylene/nitrile rubber thermoplastic elastomer blends: Application of Kerner's models for reactively compatibilized and dynamically vulcanized systems

The viscoelastic properties of binary blends of nitrile rubber (NBR) and isotactic polypropylene (PP) of different compositions have been calculated with mean‐field theories developed by Kerner. The phase morphology and geometry have been assumed, and experimental data for the component polymers over a wide temperature range have been used. Hashin's elastic–viscoelastic analogy principle is used in applying Kerner's theory of elastic systems for viscoelastic materials, namely, polymer blends. The two theoretical models used are the discrete particle model (which assumes one component as dispersed inclusions in the matrix of the other) and the polyaggregate model (in which no matrix phase but a cocontinuous structure of the two is postulated). A solution method for the coupled equations of the polyaggregate model, considering Poisson's ratio as a complex parameter, is deduced. The viscoelastic properties are determined in terms of the small‐strain dynamic storage modulus and loss tangent with a Rheovibron DDV viscoelastometer for the blends and the component polymers. Theoretical calculations are compared with the experimental small‐strain dynamic mechanical properties of the blends and their morphological characterizations. Predictions are also compared with the experimental mechanical properties of compatibilized and dynamically cured 70/30 PP/NBR blends. The results computed with the discrete particle model with PP as the matrix compare well with the experimental results for 30/70, 70/30, and 50/50 PP/NBR blends. For 70/30 and 50/50 blends, these predictions are supported by scanning electron microscopy (SEM) investigations. However, for 30/70 blends, the predictions are not in agreement with SEM results, which reveal a cocontinuous blend of the two. Predictions of the discrete particle model are poor with NBR as the matrix for all three volume fractions. A closer agreement of the predicted results for a 70/30 PP/NBR blend and the properties of a 1% maleic anhydride modified PP or 3% phenolic‐modified PP compatibilized 70/30 PP/NBR blend in the lower temperature zone has been observed. This may be explained by improved interfacial adhesion and stable phase morphology. A mixed‐cure dynamically vulcanized system gave a better agreement with the predictions with PP as the matrix than the peroxide, sulfur, and unvulcanized systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1417–1432, 2004     

Self-bonding in an amorphous polymer below the glass transition: A T-peel test investigation

Films of amorphous polystyrene (PS) with a weight-average molecular weight (M_w) of 225 × 10³ g/mol were bonded in a T-peel test geometry, and the fracture energy (G) of a PS/PS interface was measured at the ambient temperature as a function of the healing time (t_h) and healing temperature (T_h). G was found to develop with (t_h)^1/2 at T_h = T_g-bulk − 33 °C (where T_g-bulk is the glass-transition temperature of the bulk sample), and log G was found to develop with 1/T_h at T_g-bulk − 43 °C ≤ T_h ≤ T_g-bulk − 23 °C. The smallest measured value of G = 1.4 J/m² was at least one order of magnitude larger than the work of adhesion required to reversibly separate the PS surfaces. These three observations indicated that the development of G at the PS/PS interface in the temperature range investigated (<T_g-bulk) was controlled by the diffusion of chain segments feasible above the glass-transition temperature of the interfacial layer, in agreement with our previous findings for fracture stress development at several polymer/polymer interfaces well below T_g-bulk. Close values of G = 8–9 J/m² were measured for the symmetric interfaces of polydisperse PS [M_w = 225 × 10³, weight-average molecular weight/number-average molecular weight (M_w/M_n) = 3] and monodisperse PS (M_w = 200 × 10³, M_w/M_n = 1.04) after healing at T_h = T_g-bulk − 33 °C for 24 h. This implies that the self-bonding of high-molecular-weight PS at such relatively low temperatures is not governed by polydispersity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1861–1867, 2004     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004