熔融-固相缩聚法中固相聚合对聚乳酸合成的影响

以L 乳酸单体为原料 ,熔融 -固相缩聚法合成了聚乳酸 ,重点研究了固相聚合的工艺条件。结果表明 ,绝对压力 60Pa ,氯化亚锡为催化剂 ,分段控温 ,可使聚乳酸的粘均分子量提高到固相聚合反应前的 5 3倍。通过对固相聚合产物的结晶度和熔点的分析 ,探讨了固相聚合的机理。     

靳善忠副省长在全省煤炭工业工作会议上的讲话(节选)

煤炭作为山西经济发展的支柱产业，在实现全面建设小康社会的奋斗目标过程中，要做出突出贡献，任务非常艰巨，要实现这一奋斗目标，2003年要努力做好6个方面的工作，在新型煤炭工业化道路上迈出更大步伐。     

Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 Society of Chemical Industry     

Comparison of Lactic Acid Productivities at High Substrate Conversions in a Continuous Two-stage Fermenter With Cell Recycle Using Different Kinetic Models

The steady-state performance of a two-stage recycle fermenter with two different types (I and II) of configurations for staging was investigated numerically for the continuous production of lactic acid. In Type I the bleed broth withdrawn from the first stage is supplied to the second fermenter, and in Type II both filtrate and bleed broth from the first stage are introduced to the second stage. Using four different kinetic models taken from the literature, the effects of operating parameters on the overall lactic acid productivities and the overall substrate conversions are examined. At moderate conversions, productivities for Type I operation are found to be higher than those for Type II and for the single-stage system. In the case of high conversions close to complete consumption, Type II operation is more efficient than the Type I and single-stage systems. For 99% conversion and 40 kg m^-3 substrate feed concentration, productivities for Type II are predicted to be 14-74% higher compared to those for the single-stage system at the same bleed ratios.     

Continuous precipitation of calcium sulfate dihydrate from waste sulfuric acid and lime

Precipitation of calcium sulfate dihydrate, gypsum, from (i) a pure sulfuric acid/lime suspension and (ii) a waste sulfuric acid/lime suspension in a continuous pilot plant in the temperature range from 40 °C to 80 °C was studied. It was observed that in the case of waste sulfuric acid with a high content of Mg²⁺ and Fe²⁺ ions, several hours after the beginning of the precipitation, partial dissolution of the product and modification of the crystals from needle‐ and plate‐like to agglomerated structures occurred. It is suggested that the secondary changes occur due to the increased concentration of Mg²⁺ and Fe²⁺ ions in the reactor. Below 60 °C, and above 70 °C plate‐like and needle‐like single crystals respectively were formed. The mean size (d₅₀) of the crystals was found to increase with increasing temperature and decrease with the initial concentration of lime. Gypsum produced between 70 °C and 80 °C is suitable for further processing for construction plaster. In a precipitation process with pure sulfuric acid only single perfect needle‐like crystals occurred. Copyright © 2005 Society of Chemical Industry     

Rate of ammonia oxidation in a synthetic saline wastewater by a nitrifying mixed‐culture

Most of the kinetic studies on nitrification have been performed in diluted salts medium. In this work, the ammonia oxidation rate (AOR) was determined by respirometry at different ammonia (0.01 and 33.5 mg N‐NH₃ L^?1), nitrite (0–450 mg N‐NO₂^? L^?1) and nitrate (0 and 275 mg N‐NO₃^? L^?1) concentrations in a saline medium at 30 °C and pH 7.5. Sodium azide was used to uncouple the ammonia and nitrite oxidation, so as to measure independently the AOR. It was determined that ammonia causes substrate inhibition and that nitrite and nitrate exhibit product inhibition upon the AOR. The effects of ammonia, nitrite and nitrate were represented by the Andrews equation (maximal ammonia oxidation rate, r_AOMAX, = 43.2 [mg N‐NH₃ (g VSS_AO h)^?1]; half saturation constant, K_SAO, = 0.11 mg N‐NH₃ L^?1; inhibition constant K_IAO, = 7.65 mg N‐NH₃ L^?1), by the non‐competitive inhibition model (inhibition constant, K_INI, = 176 mg N‐NO₂^? L^?1) and by the partially competitive inhibition model (inhibition constant, K_INA, = 3.3 mg N‐NO₃^? L^?1; α factor = 0.24), respectively. The r_AOMAX value is smaller, and the K_SAO value larger, than the values reported in diluted salts medium; the K_IAO value is comparable to those reported. Process simulations with the kinetic model in batch nitrifying reactors showed that the inhibitory effects of nitrite and nitrate are significant for initial ammonia concentrations larger than 100 mg N‐NH₄⁺ L^?1. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of an interpenetrating polymer network composed of poly(methacrylic acid) and poly(vinyl alcohol)

Temperature and pH‐responsive interpenetrating polymer network (IPN) hydrogels, constructed with poly(methacrylic acid) (PMAA) and poly(vinyl alcohol) (PVA), by a sequential IPN method, were studied. The characterization of IPN hydrogels was investigated by Fourier‐transform infrared spectroscopy, differential scanning calorimetry (DSC) and swelling under various conditions. The IPN hydrogels exhibited relatively high swelling ratios, in the range 230–380 %, at 25 °C. The swelling ratios of the PMAA/PVA IPN hydrogels were pH and temperature dependent. DSC was used for the quantitative determination of the amounts of freezing and non‐freezing water. The amount of free water increased with increasing PMAA content in the IPN hydrogels. Copyright © 2004 Society of Chemical Industry     

Peracetic acid pretreatment of sugarcane bagasse for enzymatic hydrolysis: a continued work

Previous work has shown that the enzymatic hydrolysis of sugarcane bagasse could be greatly enhanced by peracetic acid (PAA) pretreatment. There are several factors affecting the enzymatic digestibility of the biomass, including lignin and hemicelluloses content, cellulose crystallinity, acetyl group content, accessible surface area and so on. The objective of this work is to analyze the mechanism of the enhancement of enzymatic digestibility caused by PAA pretreatment. Delignification resulted in an increase of the surface area and reduction of the irreversible absorption of cellulase, which helped to increase the enzymatic digestibility. The Fourier transform infrared (FTIR) spectrum showed that the absorption peaks of aromatic skeletal vibrations were weakened or disappeared after PAA pretreatment. However, the infrared crystallization index (N.O'KI) was increased. X‐ray diffraction (XRD) analysis indicated that the crystallinity of PAA‐treated samples was increased owing to the partial removal of amorphous lignin and hemicelluloses and probable physical change of cellulose. The effect of acetyl group content on enzymatic digestibility is negligible compared with the degree of delignification and crystallinity. The results indicate that enhancement of enzymatic digestibility of sugarcane bagasse by PAA pretreatment is achieved mainly by delignification and an increase in the surface area and exposure of cellulose fibers. Copyright © 2008 Society of Chemical Industry     

Photo-Fenton removal of water-soluble polymers

This paper presents the results of experiments carried out in a laboratory-scale photochemical reactor on the photodegradation of different polymers in aqueous solutions by the photo-Fenton process. Solutions of three polymers, polyethyleneglicol (PEG), polyacrylamide (PAM), and polyvinylpyrrolidone (PVP), were tested under different conditions. The reaction progress was evaluated by sampling and analyzing the total organic carbon concentration in solution (TOC) along the reaction time. The behavior of the different polymers is discussed, based on the evolution of the TOC–time curves. Under specific reaction conditions, the formation and coalescence of solid particles was visually observed. Solids formation occurred simultaneously to a sharp decrease in the TOC of the liquid phase. This may be favorable for the treatment of industrial wastewater containing polymers, since the photodegradation process can be coupled with solid separation systems, which may reduce the treatment cost.