Synthesis of isotactic star-shaped poly(vinyl alcohol)

Isotactic 6-armed star-shaped poly(vinyl alcohol) (PVA) with a narrow molecular weight distribution was successfully prepared by the living cationic polymerization of 6-armed star-shaped poly(tert-butyl vinyl ether) (PTBVE) and subsequent acidic ether cleavage. The PTBVE was synthesized using hexa(chloromethyl) melamine (HCMM) as a hexafunctional initiator and ZnI₂ or ZnCl₂ as an activator in toluene/MC (1/1 v/v) at −70 °C. A better living stability of PTBVE was obtained in the ZnCl₂ activator system. The number average molecular weight and the polydispersity index of the 6-armed star-shaped PTBVE polymerized with ZnCl₂ at −70 °C for 24 h were 156,000 g/mol and 1.47, respectively. The fraction of the mm sequence of the resulting PVA was 52%.     

Bacterial polyesters grafted with poly(ethylene glycol): Behaviour in aqueous media

An easy method for grafting of poly(3-hydroxyoctanoate-co-3-hydroxyundecenoate) (PHOU) was developed. Oxidation of the pendant double bonds of PHOU into carboxyl groups to yield poly(3-hydroxyoctanoate-co-3-hydroxy-9-carboxydecanoate) (PHOD) and the esterification of the carboxyl side groups with poly(ethylene glycol) (PEG) were carried out in a single reaction solution. The grafting yield is dependent on the molar mass of the PEG graft. The maximum carboxyl group conversion (52%) was obtained with PEG M_n = 350 and decreased with increasing molar mass of PEG (19% for PEG M_n = 2000). Yields were determined by ¹H and ¹³C NMR. Short PEG grafts lowered the glass transition temperature (PHOD-g-PEG 350 −57 °C) compared to PHOD (−19 °C) and PHOU (−39 °C). This effect depends on the COOH conversion and PEG chain length. Grafting enhanced the hydrophilic character of the modified polymers making them soluble in polar solvents, such as alcohols and water/acetone mixtures. PHOD-g-PEG films were more stable towards hydrolytic degradation as PHOD films. No obvious modification of films was observed after more than 200 days at pH 7.2 and 37 °C. The molar mass of the grafted polymers decreased only slightly during this period, while PHOD films were hydrolyzed into soluble fragments.     

Synthesis of new polyazines by 1,4 photochemical or anionic polymerization of 1,2-diaza-1,3-butadienes

Photochemical and anionic polymerizations of 1,2-diaza-1,3-butadienes are described. Photochemical polymerization was smoothly performed by irradiation of some 1-aminocarbonyl-1,2-diaza-1,3-butadienes with high pressure mercury arc (λ = 300 nm) in the presence of allyltributylstannane. Molecular weights (M_w) in the range 14.6-559 × 10² g/mol were obtained. The TGA curve revealed a first weight loss starting at about 200 °C of some 85%, and a second starting at about 300 °C. The DSC showed the glass transition (T_g) at about −34 °C. Anionic polymerization was performed by treatment of some 1-alkoxycarbonyl-1,2-diaza-1,3-butadienes with n-butyllithium. Molecular weights (M_w) in the range 8.44-242 × 10² g/mol were obtained.     

Bio-oil production from Onopordum acanthium L. by slow pyrolysis

In this study, the usability of the plant thistle, Onopordum acanthium L., belonging to the family Asteraceae (Compositae), in liquid fuel production has been investigated. The experiments were performed in a fixed-bed Heinze pyrolysis reactor to investigate the effects of heating rate, pyrolysis temperature and sepiolite percentage on the pyrolysis product yields and chemical compositions. Experiments were carried out in a static atmosphere with a heating rate of 7 °C/min and 40 °C/min, pyrolysis temperature of 350, 400, 500, 550 and 700 °C and particle size of 0.6 < D_p < 0.85 mm. Catalyst experiments were conducted in a static atmosphere with a heating rate of 40 °C/min, pyrolysis temperature of 550 °C and particle size of 0.6 < D_p < 0.85 mm. Bio-oil yield increased from 18.5% to 27.3% with the presence of 10% of sepiolite catalyst at pyrolysis temperature of 550 °C, with a heating rate of 40 °C/min, and particle size of 0.6 < D_p < 0.85 mm. It means that the yield of bio-oil was increased at around 48.0% after the catalyst added. Chromatographic and spectroscopic studies on the bio-oil showed that the oil obtained from O. acanthium L. could be used as a renewable fuels and chemical feedstock.     

Simultaneous distillation-extraction of high-value volatile compounds from Cistus ladanifer L

The present paper describes a procedure to isolate volatiles from rock-rose (Cistus ladanifer L.) using simultaneous distillation-extraction (SDE). High-value volatile compounds (HVVC) were selected and the influence of the extraction conditions investigated. The effect of the solvent nature and extraction time on SDE efficiency was studied. The best performance was achieved with pentane in 1 h operation. The extraction efficiencies ranged from 65% to 85% and the repeatability varied between 4% and 6% (as a CV%).The C. ladanifer SDE extracts were analysed by headspace solid phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The HS-SPME sampling conditions such as fiber coating, temperature, ionic strength and exposure time were optimized. The best results were achieved with an 85 μm polyacrylate fiber for a 60 min headspace extraction at 40 °C with 20% (w/v) of NaCl. For optimized conditions the recovery was in average higher than 90% for all compounds and the intermediate precision ranged from 4 to 9% (as CV %). The volatiles α-pinene (22.2 mg g⁻¹ of extract), 2,2,6-trimethylcyclohexanone (6.1 mg g⁻¹ of extract), borneol (3.0 mg g⁻¹ of extract) and bornyl acetate (3.9 mg g⁻¹ of extract) were identified in the SDE extracts obtained from the fresh plant material.     

Radical polymerization behavior of 3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate in water

The homogeneous polymerization of 3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate (MDAPS) with potassium peroxydisulfate (KPS) was kinetically in situ investigated in water by means of FT-near IR spectroscopy. The overall activation energy of the polymerization was calculated to be 16.0 kcal/mol. The initial polymerization rate (R_p) at 40 °C was expressed by R_p=k[KPS]^0.65[MDAPS]^1.0. The presence of alkaline metal salts was observed to accelerate the polymerization. The order of acceleration at 40 °C was CsCl > KCl > NaCl > LiCl when the chloride salts were used. NaCl showed higher acceleration effect than NaF. NaBr and NaI exhibited retardation and inhibition effect, respectively, because of reduction of KPS and its primary radical with bromide and iodide ions. The polymerization of MDAPS with KPS in water in the presence of NaCl at 2.0 mol/l gave R_p=k[KPS]^0.70[MDAPS]^1.4 at 40 °C. The overall activation energy of the polymerization in the presence of NaCl was estimated to be 11.6 kcal/mol being considerably lower value compared with that in its absence. The syndiotacticity of poly(MDAPS) tended to increase with rising temperature and decrease in the presence of NaCl.     

Thermal diffusivity measurement of low-k dielectric thin film by temperature wave analysis

Thermal diffusivity of thin film with low dielectric constant (k), what is called low-k dielectric thin film, 0.31-1.14 μm, including hydrogen-silsesquioxane (HSQ), methyl-silsesquioxane (MSQ), and poly(arylen ether) was examined by temperature wave analysis. The phase shift of temperature wave was observable up to 100 kHz. Thermal diffusivity of HSQ was 4.7 × 10⁻⁷ m² s⁻¹, on the other hand it was not higher than 1.1 × 10⁻⁷ m² s⁻¹ for MSQ or poly(arylen ether) at room temperature. Temperature dependence of thermal diffusivity/thermal conductivity of MSQ was obtained, thermal diffusivity decreased but thermal conductivity increased in a heating scan at 30-150 °C. It was shown that the thermal diffusivity of low-k thin film was correlated with the chemical and the physical structures, the latter was formed in the spin-coating and the curing process.     

Sulfide and sulfoxide based poly(ether-amide)s: Synthesis and characterization

Two new diacid monomers, 2,2′-sulfide bis(4-methyl phenoxy acetic acid) and 2,2′-sulfoxide bis(4-methyl phenoxy acetic acid) were successfully synthesized by refluxing the 2,2′-sulfide bis(4-methyl phenol) and 2,2′-sulfoxide bis(4-methyl phenol) with chloroacetonitrile in the presence of potassium carbonate, and subsequent basic reduction. Two novel series of poly(sulfide-ether-amide)s and poly(sulfoxide-ether-amide)s with aliphatic units in the main chain were prepared from diacids with various diamines.The polyamides were obtained in quantitative yields and their inherent viscosities were in the range of 0.43-0.89 dl g⁻¹ at a concentration of 0.5 g dl⁻¹ in N,N-dimethylacetamide (DMAc) solvent at 25 °C. They showed good thermal stability. The temperature for 10% weight loss in argon atmosphere was in the range of 350-415 °C. The polymers showed glass transition temperatures between 228 and 261 °C. Almost all of the polyamides were readily soluble in a variety of polar solvents such as N-methyl-2-pyrrolidone (NMP) and dimethyl sulfoxide (DMSO).     

Effects of the polymerization temperature on the structure,morphology and conductivity of polyaniline prepared with ammonium peroxodisulfate

Polyaniline (PANI) samples were prepared by the oxidation of aniline with ammonium peroxodisulfate in a reaction vessel placed in a bath thermostated to particular temperature, T_b, from −20 °C to 40 °C. Temperature–time profiles of reaction mixtures were monitored except for the reaction at −20 °C that proceeded in the solid state. The temperature regime was found to influence the molecular structure, morphology, crystallinity and electrical conductivity of PANI. The increase in T_b results in an increased content of meanwhile unspecified structure defects in the formed PANI chains (the presence of attached self-doping groups is improbable), decreased crystallinity, toughness and compactness of PANI microparticles and increased steepness of the temperature dependence of PANI conductivity. The PANI prepared in the solid-state polymerization at −20 °C shows, besides a rather high crystallinity, the unusually high position of the quinonoid band maximum: 643 nm, which suggests a high regularity of its chains. A correlation between the temperature dependence of PANI conductivity at low temperatures (range from 13 to 318 K) on one hand and the temperature regime of PANI preparation on the other hand, is reported for the first time. The dependences obtained only poorly meet the variable random hopping model.     

New soluble, thermally stable poly(amide-imide)s containing cardo anthraquinone unit

Preparation of new types of polyimides with high thermal stability and improved solubility was considered. In this way, two new amide diamines containing bulky pendant units were prepared in two steps: nucleophilic substitution reactions of 1- and 2-aminoanthraquinone with 3,5-dinitrobenzoyl chloride to form amide containing dinitro compounds, and then reduction of resulted dinitro compounds with hydrazine monohydrate in the presence of palladium/activated carbon. Two series of new poly(amide-imide)s were prepared from the reactions of these two diamines with various dianhydrides by one step polyimidation process. All poly(amide-imide)s were characterized by FTIR and ¹H-NMR spectroscopies and elemental analysis. The polymers were obtained in high yields with inherent viscosities of 0.54-0.69 dl g⁻¹. X-ray diffraction patterns (XRD) showed that all the polymers were amorphous and therefore this factor in addition to the introduction of bulky anthraquinone group led to good solubility of the polymers in most common organic solvents especially in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), and dimethylsulfoxide (DMSO). Thermal analysis showed glass transition temperature between 204 and 226 °C. Decomposition temperatures were more than 293 °C, also 10% weight loss were in the range of 387-419 °C in air.     

Polymeric salen-Ti(IV) or V(V) complex catalyzed asymmetric synthesis of O-acetylcyanohydrins from KCN, Ac2O and aldehydes

Polymeric salen-Ti(IV) and V(V) complexes were employed in the enantioselective O-acetyl cyanation of aldehydes with potassium cyanide and acetic anhydride. The crosslinked polymeric salen-Ti(IV) catalyst exhibited good activities and enantioselectivities, up to 91% ee with 99% conversion was obtained at −20 °C with 1 mol% of catalyst (based on bimetallic catalytic unit). Moreover, six consecutive recyclings with the easily recovered crosslinked polymeric catalyst showed no obvious decrease in either activity or enantioselectivity. Linear polymeric salen-V(V) catalyst showed good catalytic efficiency too, up to 94% ee with 99% conversion was obtained at −42 °C with 5 mol% of catalyst.     

InCl3-catalyzed synthesis of C-pyrrolyl glycosides via tandem condensation of aminosugars and 1,3-dicarbonyl compounds in water

Various C-pyrrolyl glycosides were obtained through tandem condensation of aminosugars (d-glucosamine and d-galactosamine) and 1,3-dicarbonyl compounds under green conditions in moderate to good yields. The reactions were carried out in the presence of 10 mol % InCl₃ in water at 50 °C. A reaction mechanism through carbocation intermediates was proposed.     

Synthesis and characterization of some novel aromatic polyimides

Three new diamines 1,2-di(p-aminophenyloxy)ethylene, 2-(4-aminophenoxy)methyl-5-aminobenzimidazole and 4,4-(aminopheyloxy) phenyl-4-aminobenzamide were synthesized and polymerized with 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BP), 4,4′-(hexafluoroisopropyledene)diphthalic anhydride (HF) and 3,4,9,10-perylene tetracarboxylic acid dianhydride (PD) either by one step solution polymerization reaction or by two step procedure. The later includes ring opening poly-addition to give poly(amic acid), followed by cyclodehydration to polyimides with the inherent viscosities 0.62-0.97 dl/g. Majority of polymers are found to be soluble in most of the organic solvents such as DMSO, DMF, DMAc, m-cresol even at room temperature and few becomes soluble on heating. The degradation temperature of the resultant polymers falls in the ranges from 240 °C to 550 °C in nitrogen (with only 10% weight loss). Specific heat capacity at 300 °C ranges from 1.1899 to 5.2541 J g⁻¹ k⁻¹. The maximum degradation temperature ranges from 250 to 620 °C. T_g values of the polyimides ranged from 168 to 254 °C.     

Thermal and mechanical properties of in situ polymerized PS/EPDM blends

In situ polymerized PS/EPDM blends were prepared by dissolving poly(ethylene-co-propylene-co-2-ethylidene-5-norbornene) (EPDM) in styrene monomer, followed by bulk polymerization at 60 °C and 80 °C . EPDM has excellent resistance to such factors as weather, ozone and oxidation, attributed to its non-conjugated diene component, and it could be a good alternative for substituting polybutadiene-based rubbers in PS toughening. The in situ polymerized blends were characterized by dynamic mechanical analysis, thermogravimetric analysis, gel permeation chromatography, and tensile and Izod impact resistance tests. The PS/EPDM blends are immiscible and present two phases, a dispersed elastomeric phase (EPDM) in a rigid PS matrix whose phase behavior is strongly affected by the polymerization temperature. Mechanical properties of the blends are influenced by the increase in the average size of EPDM domains with the increase in the polymerization temperature and EPDM content. The blends polymerized at 60 °C containing 5 wt% of EPDM presents an increase in the impact resistance of 80% and containing 17 wt% of EPDM presents an increase in the strain at break of 170% in comparison with the value of PS. The blend polymerized at 80 °C containing 17 wt% of EPDM presents an increase in the strain at break of 480% and in impact resistance of 140% in comparison with the value of PS.     

Simultaneous determination of multibenzodiazepines by HPLC/UV: Investigation of liquid-liquid and solid-phase extractions in human plasma

A method for simultaneous determination of seven benzodiazepines (BZPs) (flunitrazepam, clonazepam, oxazepam, lorazepam, chlordiazepoxide, nordiazepam and diazepam using N-desalkylflurazepam as internal standard) in human plasma using liquid-liquid and solid-phase extractions followed by high-performance liquid chromatography (HPLC) is described. The analytes were separated employing a LC-18 DB column (250 mm × 4.6 mm, 5 μm) at 35 °C under isocratic conditions using 5 mM KH₂PO₄ buffer solution pH 6.0:methanol:diethyl ether (55:40:5, v/v/v) as mobile phase at a flow rate of 0.8 mL min⁻¹. UV detection was carried out at 245 nm. Employing LLE, the best conditions were achieved with double extraction of 0.5 mL plasma using ethyl acetate and Na₂HPO₄ pH 9.5 for pH adjusting. Employing SPE, the best conditions were achieved with 0.5 mL plasma plus 3 mL 0.1 M borate buffer pH 9.5, which were then passed through a C18 cartridge previously conditioned, washed for 3 times with these solvents: 3 mL 0.1 M borate buffer pH 9.5, 4 mL Milli-Q water and 1 mL acetonitrile 5%, finally the BZPs elution was carried with diethyl ether:n-hexane:methanol (50:30:20). In both methods the solvent was evaporated at 40 °C under nitrogen flow. The validation parameters obtained in LLE were linearity range of 50-1200 ng mL⁻¹ plasma (r ≥ 0.9927), limits of quantification of 50 ng mL⁻¹ plasma, within-day and between-day CV% and E% for precision and accuracy lower than 15%, and recovery above 65% for all BZPs. In SPE, the parameter obtained were linearity range of 30-1200 ng mL⁻¹ plasma (r ≥ 0.9900), limits of quantification of 30 ng mL⁻¹ plasma, within-day and between-day CV% and E% for precision and accuracy lower than 15% and recovery above 55% for all BZPs. These extracting procedures followed by HPLC analysis showed their suitable applicability in order to examine one or more BZPs in human plasma. Moreover, it could be suggested that these procedures might be employed in various analytical applications, in special for toxicological/forensic analysis.     

Development of a temperature-responsive agarose-based ion-exchange chromatographic resin

A temperature-responsive ion-exchange resin (ItBA) has been prepared by grafting poly(N-isopropylacrylamide-co-acrylic acid-co-tert-butylacrylamide; ItBA) onto cross-linked agarose. A carboxymethylated ion exchanger (CM) of similar charge density was also prepared. Maximum adsorption capacities (B_max) for lactoferrin at 20 °C and 50 °C were determined for both resins by batch adsorption procedures. Dynamic adsorption and desorption characteristics of the CM and ItBA with lactoferrin were established, as well as the ability of ItBA to selectively adsorb and desorb lactoferrin in the presence of other proteins. With the CM-agarose resin there was no significant difference between the B_max values obtained at 20 °C and 50 °C. However, for the agarose-based ItBA resin the B_max value at 50 °C was almost three times higher than the B_max value at 20 °C. Dynamically, lactoferrin adsorbed to the ItBA packed column at 50 °C with a significant proportion of the adsorbed lactoferrin desorbed by reducing the temperature to 20 °C. In addition, anionic proteins did not adsorb to the ItBA packed column, and did not interfere with the dynamic adsorption/desorption behaviour of lactoferrin. These results indicate that this new temperature-responsive agarose-based ItBA resin has potential for the fractionation of whey proteins, with good selectivity for cationic proteins.     

Synthesis and properties of poly(aryl ether benzimidazole) copolymers for high-temperature fuel cell membranes

A series of poly(aryl ether benzimidazole) copolymers bearing different aryl ether linkage contents were synthesized by condensation polymerization in polyphosphoric acid (PPA) by varying the feed ratio of 4,4′-dicarboxydiphenyl ether (DCPE) to terephthalic acid (TA). As the ether unit content in the copolymer increased, the solubility of the copolymer in PPA and N,N′-dimethylacetamide/LiCl improved. For example 3–7 wt.% DMAc solution containing 2 wt.% of LiCl could be prepared from the copolymers. XRD studies revealed that the incorporation of flexible aryl ether linkages increased the chain d-spacings of the polymer backbones and decreased the crystallinity of the copolymers. Still, these copolymers having ether linkages showed reasonably good thermal/mechanical stability and high proton conductivity. For example, the copolymer with 30 mol% ether linkage had a tensile strength of 43 MPa (at 26 °C and 40% relative humidity) at an acid doping level of 7.5 mol H₃PO₄ and a proton conductivity of 0.098 S cm⁻¹ (at 180 °C and 0% relative humidity) at an acid doping level of 6.6 mol H₃PO₄.     

Novel thermally stable and chiral poly(amide-imide)s bearing from N,N′-(4,4′-diphthaloyl)-bis-l-isoleucine diacid: Synthesis and characterization

Novel optically active aromatic poly(amide-imide)s (PAIs) were prepared from newly synthesized N,N′-(4,4′-diphthaloyl)-bis-l-isoleucine diacid (3) via polycondensation with various diamines. The diacid was synthesized by the condensation reaction of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (1) with l-isoleucine (2) in a mixture of acetic acid and pyridine (3:2 v/v). All the polymers were obtained in quantitative yields with inherent viscosities of 0.20-0.43 dL g⁻¹. All the polymers were highly organosoluble in solvents like N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran, γ-butyrolactone, cyclohexanone and chloroform at room temperature or upon heating. These poly(amide-imide)s had glass transition temperatures between 198 and 231 °C, and their 10% weight-loss temperatures were ranging from 368 to 398 °C and 353 to 375 °C under nitrogen and air, respectively. The polyimide films had tensile strengths in the range of 63-88 MPa and tensile moduli in the range of 0.8-1.4 GPa. These poly(amide-imide)s possessed chiral properties and the specific rotations were in the range of −3.10° to −72.92°.     

The influence of chain rigidity on the thermal properties of some novel random copolyethersulfones

Some random low molar mass (M_n ≈ 9000 g mol⁻¹) poly(ethersulfoneethersulfone)/poly(ethersulfoneethersulfonebiphenylsulfone) P(ESES)/P(ESESBS) copolymers, with various (25%, 50% and 75%) ESESBS units contents, were synthesized to obtain compounds with higher chain rigidity than PES. The thermal characterization of the prepared copolymers, as well as that of corresponding P(ESES) and P(ESESBS) homopolymers, was performed, and all investigated parameters showed strong dependence on polymer composition.The glass transition temperature (T_g) was calorimetrically determined by DSC technique, and the obtained values increased linearly as function of ESESBS units percentage, thus indicating an increasing chain rigidity.Degradations were carried out in dynamic heating conditions, from 35 °C to 700 °C, in both flowing nitrogen and static air atmosphere, and the characteristic parameters of degradation were determined in order to draw useful information about the overall thermal stability of the studied compounds. The apparent activation energy of degradation (E_a) was obtained by the Kissinger method, and the values found increased linearly as a function of ESESBS content, while the temperature values at 5% mass loss (T_5%) showed an opposite linear trend. The results are discussed and interpreted.     

Optimum conditions for intercalation of lacunary tungstophosphate(V) anions into layered Ni(II)-Zn(II) hydroxyacetate

Acetate containing nickel-zinc hydroxysalts (LHS-Ni-Zn) have been synthesized by coprecipitation and hydrothermal treatment. The acetate anions were exchanged with PW₁₂O₄₀³⁻ anions, and optimum conditions to attain the maximum level of W in the compound have been identified. The W intercalated compound was characterized by powder X-ray diffraction, FT-IR spectroscopy, thermogravimetric and differential thermal analyses, scanning electron microscopy and transmission electron microscopy.The exchange of LHS-Ni-Zn with PW₁₂O₄₀³⁻ at pH=3 for 72 h leads to a solid with a basal spacing of 9.62 Å and a W content (weight) of 37%. The hydrothermal treatment at 90 °C for 24 h increases this value to 48% with a W/Zn molar ratio of 1.38, which corresponds to a layered compound with lacunary tungstophosphate anions in the interlayer space. The intercalated solid is stable up to 250 °C, the layer structure collapses on dehydroxylation and amorphous compounds were identified at 500 °C. Two crystalline phases, NiO (rock salt) and a solid solution (Zn_1−xNi_x)WO₄, were identified by powder X-ray diffraction at high temperature (ca. 1000 °C).