Fast and Living Ring-Opening Polymerization of l-Lactide Initiated with In-situ–Generated Calcium Alkoxides

The ring-opening polymerization of l-lactide with calcium alkoxides generated in-situ from bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] and 2-propanol are presented. The polymerization in THF at room temperature proceeds rapidly and in a living manner, giving poly(l-lactide)s of controlled molecular weight, low polydispersity, and tailored end-functionalities. Kinetic studies show the absence of an induction period and a pseudo-first order rate constant of 6.41 L mol^–1 min^–1, which is significantly higher than for related Y₅(-O)(O ⁱ Pr)_13– or aluminum alkoxide-initiated polymerizations. The initiation involves a two-step process: (1) alcoholysis of bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] to give the corresponding calcium alkoxide and (2) ring-opening of l-lactide via acyl-oxygen cleavage and insertion into the calcium-alkoxide bond. In the presence of excess alcohol, fast and reversible exchange between free alcohol molecules and coordinated alkoxide ligands takes place. This allows tuning of the poly(l-lactide) molecular weight over a wide range.     

Ring-Opening Polymerization of Cyclic Esters onto Liquefied Biomass

Ring-opening polymerization of cyclic esters (-caprolactone, -valerolactone, and l-lactide) onto liquefied biomass (LB) was conducted to obtain the polyester-type polyol and to regulate the characteristics of LB. IR and ¹H-NMR spectra of the obtained polyol showed that the polymerization was successfully conducted in the presence of acid catalyst, which is used in liquefaction. The molecular weight (M_w), hydroxyl value, and viscosity were controllable by changing the reaction conditions. Polyester-type polyurethane foams with a wide range of properties were prepared from the obtained polyol with the appropriate combinations of foaming agents.     

Crystallization behavior of predominantly syndiotactic poly(β-hydroxybutyrate)

Predominantly syndiotactic poly(-hydroxybutyrate), syn-PHB, of variable syndioregularity (syndyad fractions 0.59, 0.62, 0.64, and 0.71) and molecular weight was prepared by the dibutyltin dimethoxide catalyzed ring opening of racemic-butyrolactone (BL). The crystallization behavior of the syn-PHB polymers was investigated by DSC and X-ray diffraction analyses. DSC of films after melting and annealing showed at least one, and often two distinct melting transitions occuring over a broad (often 40°C) temperature range. These results indicate that syn-PHB chain segments of variable syndioregularity form crystalline regions with very different thermodynamic stabilities. Maximum degrees of crystallinity for melt annealed 0.64- and 0.71-syn-PHB was observed at an annealing temperature (T _c ) of 30°C. AtT _c values at 45°C and higher, crystallization of relatively lower syndioregular chain segments was apparently excluded to variable degrees dependent onT _c and sample syndiotactic dyad content. After crystallization of syn-PHB samples at elevated temperatures, ambient temperature annealing resulted in an observed lower temperature melting transition at 50°C. This result showed little to no dependence on syn-PHB syndio-regularity andT _c . Both solution precipitated 0.62-syn-PHB and 0.71-syn-PHB have WAXS patterns with poorly resolved crystalline reflections superimposed on amorphous haloes indicating low levels of crystallinity (17% and 25%, respectively) and poorly formed crystals. Isothermal crystallization monitored by DSC showed that the syn- and natural origin PHB showed fastest crystallization rates at temperatures between 50°C and 70°C and 60°C and 90°C, respectively. From the dependence of the higher melting transition onT _c it was determined that the equilibrium melting temperatures for 0.62-syn-PHB (M _n =83,700 g/mol) and a 0.64-syn-PHB (M _n =11,900 g/mol) were 157 and 154°C, respectively. An Avrami analysis of syn-PHB yielded results similar to that found for natural origin PHB indicating that crystal growth occurs by a two-dimensional mechanism.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Synthesis of a block copolymer of poly(3-hydroxybutyrate) and poly(ethylene glycol) and its application to biodegradable polymer blends

A block copolymer {P[(R,S)-HB-b-EG]} of atactic poly[(R,S)-3-hydroxybutyrate] {P[(R,S)-HB]} and poly(ethylene glycol) (PEG) was prepared by the ring-opening polymerization of -butyrolactone in the presence of a macroinitiator (PEG/ZnEt₂/H₂O) which had been produced by the reaction of ,-dihydroxy PEG ( _n=3000) with ZnEt₂/H₂O (1/0.6) catalyst. The block copolymer ( _n=10,500, _w/ _n=1.2) was an A-B-A triblock copolymer comprising atactic P[(R,S)-HB] (A) and PEG (B) segments. The miscibility, physical properties, and biodegradability of binary blends of microbial poly[(R)-3-hydroxybutyrate] {P[(R)-HB]} with the block copolymer P[(R,S)-HB-b-EG] has been studied. The glass-transition temperature (T _g) data showed that the P[(R)-HB]/P[(R,S)-HB-b-EG] blend was miscible in the amorphous state. The P[(R)-HB] film became flexible and tough by means of blending with P[(R,S)-HB-b-EG] block copolymer. The enzymatic degradation of blend films was carried out at 37°C and pH 7.4 in a 0.1M phosphate solution of an extracellular PHB depolymerase fromAlcaligenes faecalis. The enzymatic degradation took place solely on the surface of the blend films.     

Degradation of Cellulosic Materials Under the Alkaline Conditions of a Cementitious Repository for Low- and Intermediate-Level Radioactive Waste. II. Degradation Kinetics

The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are - and -(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.     

Styrene/Lignin-Based Polymeric Composites Obtained Through a Sequential Mass-Suspension Polymerization Process

A modified sequential mass-suspension polymerization was employed to ensure adequate dispersion of lignin into the monomeric phase. Due to its complex macromolecular structure and low compatibility with styrene, eucalyptus wood-extracted lignin, via a modified Kraft method, was esterified with methacrylic anhydride to ensure organic phase homogeneity into the reaction medium. Infrared spectroscopy showed a decrease in the hydroxyl band, a characteristic of natural lignin (3200–3400 cm^?1) and an increase in the characteristic ester band (1720–1740 cm^?1) whereas nuclear magnetic resonance measurements exhibited intense peaks in the range from 1.7 to 2.05 ppm (–CH₃) and 5.4 to 6.2 ppm (=CH₂), related to methacrylic anhydride. Comparatively, the esterified lignin also displayed an increase of its glass transition temperature for 98?°C, related to natural lignin, whose T _g was determined to be equal to 91?°C. Styrene/lignin-based polymers exhibited higher average molar masses in comparison to the values observed for polystyrene synthesized with similar amounts of benzoyl peroxide, due to the ability of lignin to act as a free-radical scavenger. Composites obtained with styrene and natural or esterified lignin were successfully synthesized, presenting regular morphology and proper lignin dispersion. Based on a very simple polymerization system, it is possible to enhance the final properties of polystyrene through the incorporation of lignin, which represents an important platform for developing attractive polymeric materials from renewable resources.     

阳离子乳液型清水剂的制备及其在油田污水处理中的应用

以二甲基二烯丙基氯化铵(DMDAAC)为阳离子单体,苯乙烯、丙烯酸丁酯为疏水单体,十六烷基三甲基溴化铵和聚氧乙烯辛基苯酚醚-10(OP-10)为乳化剂,过硫酸铵为引发剂,采用乳液聚合法制备乳液型清水剂。优化了制备清水剂的工艺条件,考察了清水剂对油田污水的处理效果。实验结果表明:在x(DMDAAC)小于20%、n(苯乙烯)∶n(丙烯酸丁酯)为2∶1、乳化剂占单体质量分数为5%、引发剂占单体质量分数为0.5%的优化条件下可制备形成稳定的阳离子乳液清水剂;分子量越大、x(DMDAAC)越大,清水剂的除油效果越好;在x(DMDAAC)为20%、其他最优条件不变的情况下制备的Q20清水剂使用浓度为30 mg/L时可使油田污水含油量从295 mg/L降至13 mg/L。自制清水剂的除油效果好于市售清水剂。     

Preparation of Soybean Oil Polymers with High Molecular Weight

The cationic polymerization of soybean oils was initiated by boron trifluoride diethyl etherate in supercritical carbon dioxide medium. The resulting polymers had molecular weight ranging from 21,842 to 118,300 g/mol. Nuclear magnetic resonance spectroscopy and gel permeation chromatography analysis confirmed the polymerization had occurred. Parameters affecting the polymerization were studied, which included initiator amount and reaction time. Results show that the longer reaction time, up to 3 h, favored the higher molecular weight of polymers at conditions of 140 °C and initiator BF₃·OEt₂ (2.5 g, 0.018 mol). When reaction time was increased further, the molecular weight of polymers stayed the same or slightly decreased. Increased concentration of initiator gave the higher molecular weight of polymers. The high molecular weight polymers were possibly formed through two path ways: polymerization and intermolecular Diels-Alder reaction.     

Air Pollution Zones and Harmful Pollution Levels of Alkaline Dust for Plants

For characterisation of landscapes in north-eastern Estoniaaffected by alkaline oil shale fly ash and cement dust the zonation-method based on average annual (C _y) and short-termconcentrations of pollutants in the air was used, as well as on deposition loads of dust and Ca²⁺. In the overground layer of atmosphere the zones with different air pollution loads were distinguished. A comparative analysis of pollution zones characteristics and biomonitoring data revealed that for sensitive lichen the dangerous level of alkaline dust in the air, introducingthe degradation of Sphagnum sp. at the level of C _y of dust 10–20 g m^-3 and at 0.5–1 hr maximums 100–150 g m^-3. For Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies (L.) Karst.) this limited concentration (decline of growth parameters) of cement dust is correspondingly following: 30–50 g m^-3 and 150–500 g m^-3, in case of fly ash the limit level of C _y amounting 100 g m^-3. Daily deposition load of Ca²⁺ should not exceed approximately 4.5–15 mg m^-2 for lichen; for conifers the harmful pollution load is higher – >22 mg m^-2.     

Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Itaconic Acid Grafted Starch Hydrogels as Metal Remover: Capacity,Selectivity and Adsorption Kinetics

Hydrogels were synthesized by free radical graft copolymerization of itaconic acid (IA) onto corn starch (S-g-IA). For this purpose, potassium permanganate (KMnO₄)-sodium bisulfite (NaHSO₃) was used as redox initiation system. The formation of grafted starches was confirmed by Fourier transform infrared spectroscopy, wide angle X-ray scattering, thermogravimetric analysis and scanning electron microscopy. The effect of monomer concentration, neutralization, addition of crosslinking agent, N,N-bismetilenacrilamide (MBAm), and initiator concentration on grafting efficiency and adsorption capacity of the starch hydrogels was investigated. It was demonstrated that the introduction of carboxyl and carbonyl groups promoted starch hydration and swelling. Grafting degree increased with the decrease of monomer concentration, increase of initiator concentration, grade of neutralization and the addition of MBAm without neutralization. Remarkably the resulting materials exhibited water absorption capacities between 258 and 1878% and the ability to adsorb metal ions. It was experimentally confirmed the metal uptake, obtaining the higher adsorption capacity (q _e  = 35 mg/g) for the product prepared with the pre-oxidation and lower initiator concentration. The removal capacity order was Pb²⁺>Ni²⁺>Zn²⁺>Cd²⁺. Moreover, the experimental kinetic and the equilibrium adsorption data for Ni²⁺ and Pb²⁺ were best fitted to the pseudo-second order and Freundlich isotherm models, respectively. This work describes for the first time the preparation of metal removal hydrogels based on starch and itaconic acid using the pair redox system KMnO₄/NaHSO₃, which avoids the starch hydrolysis and allows itaconic acid grafting incorporation without the requirement of more reactive comonomers.     

Application of the rescue number to the evaluation of remediation technologies for contaminated ground

An improved rescue number, RN_SOIL, which is an indicator for evaluating remediation technologies for contaminated ground that is based on both the risk and the remediation cost, is proposed as a tool of risk communication. The risk posed by contaminated ground is indicated by the figure of treatment priority at time t, FTP(t), which represents the human health risk as the number of people affected by the contaminated ground at time t during the remediation process. The calculation of the value of FTP(t) is based on exposure to contaminants that have migrated through environmental media from the contaminated ground, and is estimated by using a CalTOX model and the Monte Carlo method. The integration of FTP(t) with time, which represents the cumulative number of people affected by the contaminated ground, is used to estimate the performance of individual remediation technologies in risk reduction. The figure of unprocessibility for waste (FUW), which represents difficulties in remediation, is expressed as the remediation cost. FUW is estimated by using actual costs per unit volume of remediated soil. As an overall performance value, the rescue number for each remediation technology for contaminated ground (RN_SOIL) is calculated by multiplication of the integral FTP(t) by FUW. Smaller values of RN_SOIL are judged to indicate a better technology. The rescue index (RI), calculated as the ratio of the reduction of the integral FTP(t) to FUW, indicates the cost-effectiveness of the remediation technologies. Successful estimation of the indices (FTP(t), integral FTP(t), FUW, RN_SOIL and RI) demonstrate the usefulness of these indices in risk communication.Part of this paper was presented at 13th meeting of Japan Society of Waste Management Experts (2002)     

Correction Factors for Covariance between Concentration and Deposition Velocity on CASTNes HNO3 Deposition Estimates

The covariance between hourly concentration (C) and depositionvelocity (V) for various atmospheric species may act to bias the dry deposition (D) computed from the product of the weeklyaverage C and V. This is a potential problem for the CASTNet filter pack (FP) species, nitric acid (HNO₃). Using ozone (O₃) behavior as a surrogate for HNO₃, correctionfactors (CF) are developed to estimate this bias. Weekly CF for O₃ depend on both site and season, and seasonal average weekly CF for O₃ at a given site may be as high as 1.25.The seasonal magnitude of this CF is generally largest in summerand is ordered: summer fall spring > winter. The CF is drivento a large extent by the diurnal correlation between C andV (i.e., both are generally higher during the day and lower at night). However, since the diurnal C profile at elevated sites is relatively constant, the resulting correlation between C and V is small, and the CF at montane sites is generally negligiblysmall. The sampling protocol using daytime integrated sampling for a week and nighttime integrated sampling for a week capturesthe diurnal correlation between C and V adequately and may be used to aggregate relatively unbiased weekly D estimates. Day-night CF for O₃ are close to unity, and limited results suggest similar behavior for HNO₃. Using these limited FP results, the site- and seasonally-specific weekly CF forO₃are refined to estimate the corresponding CF for HNO₃. Worst-case adjustments for HNO₃ as high as 30% are indicated for summer periods at a given site.     

The Control of SO2 Dry Deposition on to Natural Surfaces by NH3 and its Effects on Regional Deposition

Two years of continuous measurements of SO₂deposition fluxes to moorland vegetation are reported. The mean flux of 2.8 ng SO₂ m^-2 s^-1 is regulated predominantly by surface resistance (r _c) which, even for wet surfaces, was seldom smaller than 100 s m^-1. The control of surface resistance is shown to be regulated by the ratio of NH₃SO₂ concentrations with an excess of NH₃ generating the small surface resistances for SO₂. A dynamic surface chemistry model is used to simulate the effects of NH₃ on SO₂ deposition flux and is able to capture responses to short-term changes in ambient concentrations of SO₂, NH₃ and meteorological conditions. The coupling between surface resistance and NH₃/SO₂ concentration ratios shows that the deposition velocity for SO₂ is regulated by the regional pollution climate. Recent long-term SO₂ flux measurements in a transect over Europe demonstrate the close link between NH₃/SO₂ concentrations and rc (SO₂). The deposition velocity for SO₂ is predicted to have increased with time since the 1970s and imply a 40% increase in v _d at a site at which the annual mean ambient SO₂ concentrations declined from 47 to 3 g m^-3 between 1973 and 1998.     

Syntheses of Biodegradable Functional Polymers by Radical Ring-Opening Polymerization of 2-Methylene-1,3,6-trioxocane

2-Methylene-1,3,6-trioxocane (MTC) was polymerized via ring-opening in the presence of a radical initiator and the obtained polyester was biodegradable. MTC could also copolymerize with various vinyl monomers such as styrene, vinyl acetate, methyl vinyl ketone, N-vinyl-2-pyrrolidone, N-isopropyl acrylamide, and maleic anhydride. By copolymerizing MTC with these vinyl monomers in the presence of a radical initiator, we could obtain various biodegradable polymers with ester group introduced into the backbone. In addition the obtained copolymers exhibit certain functionalities such as photolysis, water-solubility, thermosensitivity, detergent builder, and water-absorbability.     

Correlating the Spatial Distribution of Atmospheric Ammonia with δ15N Values at an Ammonia Release Site

A field ammonia (NH₃) release experiment and open top chambers containing moorland monoliths continuously fumigated with NH₃ or sprayed with NH₄Cl were used to assess the potential for using ¹⁵N values in determining the area of influence around a point NH₃ emission source. ¹⁵N values are being increasingly used as environmental tracers and we tested the hypothesis that the ¹⁵N signal from an NH₃ emission source is observable in nearby vegetation. Using modified monitoring devices, atmospheric NH₃ concentrations were found to decrease with distance from source, with ¹⁵N values also reflecting this trend, producing a signal shift with changing concentration. Open top chamber studies of ¹⁵N values of Calluna vulgaris (L.) Hull indicated a correlation with deposition treatments in current year shoots. Analysis of Calluna shoots from the NH₃ release showed a similar trend of ¹⁵N enrichment. Significant linear correlations between ¹⁵N and percent N in plant material were found, both in the controlled conditions of the open top chambers and at the NH₃ release site, illustrating the possible use of this technique in N deposition biomonitoring.     

Preparation and Characterization of Polyaniline and Ag/ Polyaniline Composite Nanoporous Particles and Their Antimicrobial Activities

Polyaniline (PANI) and Ag/PANI nanoporous composite were prepared by an oxidative polymerization method. The oxidation process of PANI nanoparticles was occurred using (NH₄)₂S₂O₈ while the oxidation process of Ag/PANI nanoporous composite was occurred using AgNO₃ under the effect of artificial radiation. The structural, morphological, and optical properties of the PANI and Ag/PANI nanoporous structures were studied using different characterization tools. The results confirm the formation of polycrystalline nanoporous PANI and spherical nanoporous composite of Ag/PANI particles. Antibacterial activity tests against gram-positive bacteria, Bacillus subtilis and Staphylococcus aureus, and gram-negative bacteria, Escherichia coli, and Salmonella species were carried out using different concentrations of PANI nanoparticles and Ag/PANI nanoporous composites. PANI has not antibacterial effect against all studied pathogens. In contrast, Ag/PANI nanoporous composites possessed antibacterial activity that is identified by the zone of inhibition. The inhibition zones of bacteria are in order; Salmonella species?>?S. aureus?>?B. subtilis?>?E. coli. The inhibition zones of all bacteria increased with increasing concentrations of Ag/PANI nanoporous composites from 200 to 400 ppm then decreased with further increasing of the dose concentrations to 600 ppm. Finally, a simplified mechanism based on the electrostatic attraction is presented to describe the antimicrobial activity of Ag/PANI nanoporous composite.     

Monitoring degradation of poly(hydroxybutyrate) by fracture toughness measurements

The fracture behavior of poly(hydroxybutyrate) is described in terms of classical fracture mechanics. The fracture toughness (measured byG _c, the strain energy release rate, andK _c, the stress intensity factor) was monitored during physical aging and during chemical degradation with methylamine. A change in the measuredK _c value was found after degradation by methylamine which does not seem to be due solely to the measured thickness changes. The work lays the foundation for studies monitoring changes in fracture behavior during environmental degradation.Presented at the 4th International Workshop on Biodegradable Plastics and Polymers, October 11–14, 1995. Durham, New Hampshire.     

Biodegradation of Polyaromatics Synthesized by Peroxidase-Catalyzed Free-Radical Polymerization

Polymers formed from peroxidase-based free-radical polymerization reactions were characterized for rates of mineralization against lignin and humic acid controls. Degradation studies were carried out in soil systems over 202 days and cumulative net CO₂ was determined. Whereas mineralization of the humic acid and alkali lignin controls totaled ca. 20% at the end of the test exposure, there was essentially no net mineralization of the hydrolytic lignin control. Mineralization of the test samples totaled 5% for poly(p-ethylphenol) and 11% for poly(m-cresol). At the same time, mineralization of the poly(p-phenyl phenol) totaled 64%. Conversely, the readily biodegradable polymers cellulose and PHB reached values of 91 to 97% in less than 60 days. Our data suggest that the mineralization kinetics of the enzymatically derived polyaromatics mimic those of the naturally occurring heteropolymers.     

Hysteresis in Reversal of Central European Mountain Lakes from Atmospheric Acidification

Extremely high emissions of S and N compounds in Central Europe (both 280 mmol m^-2 yr^-1) declined by 70and 35%, respectively, during the last decade. Decreaseddeposition rates of SO₄ ^-2, NO₃ ^-, and NH₄ ⁺ in the region paralleled emission declines. The reduction in atmospheric inputs of S and N to mountain ecosystemshas resulted in a pronounced reversal of acidification in the Tatra Mountains and Bohemian Forest lakes. Between the 1987–1990and 1997–1999 periods, concentrations of SO₄ ^-2 and NO₃ ^- decreased (average ± standard deviation) by 22±7 and 12±7 mol L^-1, respectively, in theTatra Mountains, and by 19±7 and 15±10 mol L^-1, respectively, in the Bohemian Forest. Their decrease was compensated in part (1) by a decrease in Ca²⁺ + Mg²⁺ (17±7 mol L^-1) and H⁺ (4±6 mol L^-1), and an increase in HCO₃ ^-(10±10 mol L^-1) in the Tatra Mountains lakes, and (2) by a decrease in Al (7±4 mol L^-1), Ca²⁺ + Mg²⁺ (9±6 mol L^-1), and H⁺ (6±5 mol L^-1), in Bohemian Forest lakes. Despite the rapid decline in lake water concentrations of SO₄ ^-2 and NO₃ ^- in response to reduced S and N emissions, their present concentrations in some lakes are higher than predictionsbased on observed concentrations at comparable emission rates during development of acidification. This hysteresis in chemical reversal from acidification has delayed biological recovery of the lakes. The only unequivocal sign of biological recovery hasbeen observed in erné Lake (Bohemian Forest) where a cladoceran species Ceriodaphnia quadrangular has recentlyreached its pre-acidification abundance.