对苯二甲酸邻菲罗啉铈镧配合物的荧光光谱研究

用对-苯二甲酸铵和邻菲罗啉与氯化铈和氯化镧在无水乙醇溶液中反应,合成了稀土三元配合物,研究了红外光谱、紫外光谱和荧光光谱。结果表明,羟基氧和邻菲罗啉氮原子与稀土离子配位,不发光的La^(3+)时Ce^(3+)的荧光强度有增强作用,是因为配体对-苯二甲酸根有效的传送能量。

对－苯二甲酸衍生物的合成及其诱导分化HL－60细胞的活性

作者合成了１３个对－苯二甲酸衍生物，其中有９个化合物尚未见文献报道。通过对ＨＬ－６０细胞诱导分化活性试验，发现有两个化合物在浓度为５×１０￣（－６）ｍｏｌ／Ｌ时，可使细胞分化率达５５％，低于维Ａ酸的分化率（７９％，１０￣（－７）ｍｏｌ／Ｌ）。

高效液相色谱法测定精对苯二甲酸中微量杂质

建立了高效液相色谱法 (HPLC)同时测定精对 苯二甲酸 (PTA)中微量杂质 4 羧基苯甲醛 (4 CBA)、对 甲基苯甲酸 (P TOL)和苯甲酸 (C7H6O2 )含量的方法 .采用的色谱柱为Shim PackWAX 1柱 ,流动相为 0 .1mol/LNH3 H2 PO4+6 %CH3 OH ,(pH 4 .5 ) ,检测波长为 2 5 4nm .PTA中微量杂质 4 CBA、P TOL和C7H6O2 的含量分别为 0 .5 9～ 2 35 .2 0mg/kg、4 .5 2～ 392 .0 0mg/kg和 0 .2 8～ 2 4 .5 5mg/kg时线性关系良好 ,其线性相关系数分别为 0 .9998、0 .9997和 0 .9999.苯甲酸加样平均回收率 99.0 3% ,RSD 0 .37% .

IN-SITU POLYMERIZED SYNTHESIS AND PROPERTIES OF NANO-ZnO/PEG/PET COMPOSITE

Nano-ZnO particle （nZnOp） reinforced polyethylene glycol （PEG）/polyethylene terephthalate （PET） （nZnOp/PEG/PET） copolymeric composites with different mass fractions and molecular weights of PEG are synthesized via in-situ polymerization. The dispersion of nZnOp in copolymer matrixes and the effects of PEG and nZnOp particles on the crystallization behavior of the composites are studied by TEM, differential scanning calorimetry（DSC）, XRD and Fourier thansform infrared spectroscopy （FTIR ）. The results reveal that nZnOp particles are dispersed in the matrixes with nano-scale, and the addition of PEG induces more homogeneous dispersion of nZnOp. Simultaneously, these nanoparticles become nucleating centers during the crystallization of the matrixes. PEG segments can improve the flexibility of the PET molecular chain, resulting in the drop of the cold crystallization temperature and the rise of the crystallization rate of the composites. Furthermore, PEG （4 000） with the mass fraction of 10% can promote the crystallization rate of the composites. The mechanical properties show that the nano-particles strengthen and toughen the PET matrix, whereas PEG weakens these improve- ments.

STUDY ON SYNTHESIS OF p-TOLUIDINE-o-SULFONIC ACID

Synthesis of p toluidine o sulfonic acid from p toluidine by sulfonation in solvent was studied,and effects of various reaction conditions or factors on the reaction were discussed in detail.As a result,the following optimum process conditions are presented:50 mL dichlorobenzene,2%～5% oleum,molar ratio of sulfonating agent to p toluidine is 1.10～1.12,oleum is dropped in the reaction system in 10 min or so,sulfate formation time is 2 h,distillation lasts 8 h.Under the above conditions,the purity and the yield of p toluidine o sulfonic acid are better than that of the same product made in Japan.

Alkylpolyglycoside inducing poly (butylene terephthalate) non-woven graft copolymerization of chitosan

In order to improve the wettability and biocompatibility of the poly （butylene terephthalate） non-woven （PBTNW）, the method of surface modification is used to graft copolymerization of chitosan （CS） onto the PBTNW under alkylpolyglycoside （APG） inducing. The product is thoroughly characterized with the Fourier transform infrared spectroscopy （FrIR）, the electron spectroscopy for chemical analysis （ESCA）, the thermogravimetric （TG） and the scanning electron microscopy （SEM）. It is found that chitosan is successfully grafted onto PBTNW. In addition, the water contact angles, hemolysis tests and cytotoxicity evaluation tests show an improvement in wettability and biocompatihility as a result of graft copolymerization of chitosan. So the CS-grafted PBTNW exhibits greater superiority than the original PBTNW. The CS-grafted PBTNW can be a candidate for blood filter materials and other medical applications.

Multi-objective Optimization of Industrial Purified Terephthalic Acid Oxidation Process

Multi-objective optimization of a purified terephthalic acid (PTA) oxidation unit is carried out in this paper by using a process modei that has been proved to describe industrial process quite well. The modei is a semi-empirical structured into two series ideal continuously stirred tank reactor (CSTR) models. The optimal objectives include maximizing the yield or inlet rate and minimizing the concentration of 4-carboxy-benzaldhyde, which is the main undesirable intermediate product in the reaction process. The multi-objective optimization algorithra applied in this study is non-dominated sorting genetic algorithm Ⅱ (NSGA-Ⅱ). The performance of NSGA-Ⅱ is further illustrated by application to the title process.

Fuzzy Support Vector Regression Model of 4-CBA Concentration for Industrial PTA Oxidation Process

In the past few years, support vector machines (SVMs) have been applied to many fields, such as pattern recognition and data mining, etc. However there still exist some problems to be solved. One of them is that the SVM is very sensitive to outliers or noises because of over-fitting problem. In this paper, a fuzzy support vector regression (FSVR) method is presented to deal with this problem. Strategies based on k nearest neighbor (kNN) and support vector data description (SVDD) are adopted to set the fuzzy membership values of data points in FSVR.The proposed FSVR soft sensor models based on kNN and SVDD are employed to predict the concentration of 4-carboxy-benzaldehyde (4-CBA) in purified terephthalic acid (PTA) oxidation process. Simulation results indicate that the proposed method indeed reduces the effect of outliers and yields higher accuracy.

In-situ Polymerization-modification Process and Foaming of Poly（ethylene terephthalate）

Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support and keep cells.An in-situ polymerization-modification process with esterification and polycondensation stages was performed in a 2 L batch stirred reactor using pyromellitic dianhydride(PMDA)or pentaerythritol(PENTA)as modifying monomers to obtain PETs with high melt strength.The influence of amounts of modifying monomers on the properties of modified PET was investigated.It was found that the selected modifying monomers could effectively introduce branched structures into the modified PETs and improve their melt strength.With increasing the amount of the modifying monomer,the melt strength of the modified PET increased.But when the amount of PENTA reached 0.35%or PMDA reached 0.9%,crosslinking phenomenon was observed in the modified PET.Supercritical carbon dioxide(ScCO2)was employed as physical foaming agent to evaluate the foaming ability of modified PETs.The modified PETs had good foaming properties at 14 MPa of CO2pressure with foaming temperature ranging from 265°C to 280°C.SEM micrographs demonstrated that both modified PET foams had homogeneous cellular structures,with cell diameter ranging from 35μm to 49μm for PENTA modified PETs and38μm to 57μm for PMDA modified ones.Correspondingly,the cell density had a range of 3.5×107cells·cm 3to 7×106cells·cm 3for the former and 2.8×107cells·cm 3to 5.8×106cells·cm 3for the latter.

4-CBA Soft Sensor Based on Fuzzy CMAC Neural Networks

Soft sensor is attractive in dealing with online product quality measurement by virtue of other easily measured variables. In AMOCO PTA (purified terephthalic acid) production process, the unavailability of real-time measurement of 4-CBA makes it impossible for timely adjustment and thereby influences the product quality and the plant economy benefit. In this paper, a kind of FCMAC (fuzzy cerebellar model articulation controller) method is presented to solve the online measurement problem. Different from the conventional CMAC (cerebellar model articulation controller) networks, which has inferior smoothing ability because of its table look-up based technology. Integrating fuzzy model into CMAC networks, it becomes more accurate in functional mapping without weakening its generalization ability. Numerical example and industrial application results show the method proposed here is satisfactory and feasible.

Preparation and Properties of a New Type of Poly(butylene-terephthalate)with Layered Silicate Nanocomposites

In this paper, poly(butylene-terephthalate)-layered silicate of clay nanocomposites (NPBT) are reported. Their thermal properties, heat distortion temperature (HDT) and crystallization nucleation are investigated. NPBT samples have apparent viscosity over 0.85, HDT of 30℃ to 50℃ higher than that of poly (butylene-terephthalate) (PBT) for clay load from 1.0% to 10.0% (by mass), and higher capability to accommodate clay than other polymers. The nonisothermal crystallization experiments indicate that the better thermal degradation behavior and crystallization rate of NPBT are 50% higher than PBT, and its injection mould processing temperature is lowered from 110℃ to 55℃. NPBT samples are characterized by several techniques. X-ray shows an original clay interlayer distance enlarged from 1.0 nm to 2.5 nm, while both TBM and AFM indicate an average size from 30nm to lOOnm of exfoliated clay layers, and 3%(by mass) of particle agglomeration being phase separated from PBT matrix, which are factors on some mechanical properties decrease of NPBT. The disappearance of spherulitic morphology in NPBT resulted from layers nucleation is detected. Improving NPBT properties by treating clay with long chain organic reagent and controlling the way to load it is suggested.

Synergistic Catalytic Action of Cobalt(Ⅱ) Hydroxamates and N-Hydroxyphthalimide in the Aerobic Oxidation of p-Xylene

The catalytic performance of a series of cobalt(Ⅱ) hydroxamates (CoL2) and the synergistic catalytic action of the cobalt complexes combined with N-hydroxyphthalimide (NHPI) in the aerobic oxidation of p-xylene to p-toluic acid (PTA) were investigated. The results showed that the existing synergistic action in the catalytic oxidation can shorten the induction period of the radical reaction and improve the yield of PTA.

Soft sensor of chemical processes with large numbers of input parameters using auto-associative hierarchical neural network

To explore the problems of monitoring chemical processes with large numbers of input parameters, a method based on Auto-associative Hierarchical Neural Network(AHNN) is proposed. AHNN focuses on dealing with datasets in high-dimension. AHNNs consist of two parts: groups of subnets based on well trained Autoassociative Neural Networks(AANNs) and a main net. The subnets play an important role on the performance of AHNN. A simple but effective method of designing the subnets is developed in this paper. In this method,the subnets are designed according to the classification of the data attributes. For getting the classification, an effective method called Extension Data Attributes Classification(EDAC) is adopted. Soft sensor using AHNN based on EDAC(EDAC-AHNN) is introduced. As a case study, the production data of Purified Terephthalic Acid(PTA) solvent system are selected to examine the proposed model. The results of the EDAC-AHNN model are compared with the experimental data extracted from the literature, which shows the efficiency of the proposed model.

Nonisothermal Crystallization Kinetics of Poly(butylene adipate-co-terephthalate) Copolyester

Nonisothermal crystallization behavior of poly(butylene adipate-co-terephthalate)(PBAT) synthesized via direct esterification and polycondensation reactions was investigated by the differential scanning calorimetry(DSC).The Avrami equation modified by Jeziorny and the Z.S.Mo equation were employed to describe the non-isothermal crystallization kinetics of copolyester samples.The test results showed that the Avrami equation was successful in describing nonisothermal crystallization process of PBAT copolyesters.PBAT copolyester could give birth to secondary crystallization.The crystallization parameter(Zc) increased with an increasing cooling rate and the Avrami exponent(n) was around 2.3.For a given cooling rate,the value of Zc demonstrated a sagging trend with an increase in adipic acid(AA) content.The equation proposed by Z.S.Mo was successful in describing the nonisothermal crystallization kinetics of PBAT copolyesters.

Study on Morphology and Non-isothermal Crystallization Behavior of Poly(phenylene sulfide)/Poly(ethylene-co-cyclo-hexane 1,4-dimethanol terephthalate) Blend

A binary alloy consisting of poly（phenylene-sulfide） （PPS）/poly（ethylene terephthalate-co-l,4- cyclohexanedimethanol） （PETG） was prepared by the melt blending technology using a twin-screw extruder. The morphology and crystallization behavior of the alloy material were investigated by means of SEM, POM and DSC. The SEM study of the alloy samples revealed that PPS and PETG comprised an incompatible system and the interface structure of two phases could be observed distinctly when the composition of the binary alloy was being changed. The POM results had revealed that incorporation of PETG into PPS could lead to formation of larger spherulite crystals in the course of PPS crystallization, but small and grainy spherulite crystals appeared with further increase in the PETG concentration. The DSC analyses revealed that addition of PETG to the alloy composition could shift the PPS crystallization temperature towards the high-temperature region.

Excess Molar Volume, Viscosity and Heat Capacity for the Binary Mixture of p-Xylene and Acetic Acid at Different Temperatures

Experimental densities, viscosities and heat capacities atdifferent temperatures were presented over the entire range of molefraction for the binary mixture of p-xylene and acetic acid. Densityvalues were used in the determination of excess molar volumes, V^E.At the same time, the excess viscosity and excess molar heatcapacities were calculated. The values of V^E, η~E and c^E_p werefitted to the Redlich-Kister equation. Good agreements were observed.The excess molar volumes are positive with a large maximum valuelocated in the central concentration range.

Heterogeneity of Adsorption Sites and Adsorption Kinetics of n-Hexane on Metal–Organic Framework MIL-101(Cr)

The heterogeneity of adsorption sites and adsorption kinetics of n-hexane on a chromium terephthalate-based metal-organic framework MIL-10^1 （Cr） were studied by gravimetric method and temperature-programmed desorption （TPD） experiments. The MIL-101 crystals were synthesized by microwave irradiation method. The ad- sorption isotherms and kinetic curves of n-hexane on the MIL-101 were measured. Desorption activation energies of n-hexane from the MIL-10^1 were estimated by TPD experiments. The resulthowed that equilibrium amount ofn-hexane adsorbed on the MIL-10^1 was up to 5.62 mmol.g- 1 at 298 K and 1.6 x10^4 Pa, much higher than that of some activated carbons, zeolltes and so on. The isotherms of n-hexane on the MIL-101 could be well fitted with Langmuir-Freundlich model. TPD spectra exhibit two types of adsorption sites on the MIL-101 with desorption activation energies of 39.41 and 86.69 kJ. mol-1. It reflects the surface energy heterogeneity on the MIL-10I frameworks for n-hexane adsorption. The diffusion coefficients of n-hexane are in the range of （1.35- 2.35 ） x 10 - 1 o cm2. s - 1 with ad sorotion activation enerv of 16.33 kl. mol - 1.

High dimension feature extraction based visualized SOM fault diagnosis method and its application in p-xylene oxidation process

Purified terephthalic acid(PTA) is an important chemical raw material. P-xylene(PX) is transformed to terephthalic acid(TA) through oxidation process and TA is refined to produce PTA. The PX oxidation reaction is a complex process involving three-phase reaction of gas, liquid and solid. To monitor the process and to improve the product quality, as well as to visualize the fault type clearly, a fault diagnosis method based on selforganizing map(SOM) and high dimensional feature extraction method, local tangent space alignment(LTSA),is proposed. In this method, LTSA can reduce the dimension and keep the topology information simultaneously,and SOM distinguishes various states on the output map. Monitoring results of PX oxidation reaction process indicate that the LTSA–SOM can well detect and visualize the fault type.

An agent-based service-oriented integration architecture for chemical process automation

In reality, traditional process control system built upon centralized and hierarchical structures presents a weak response to change and is easy to shut down by single failure. Aiming at these problems, a new agent-based service-oriented integration architecture was proposed for chemical process automation system. Web services were dynamically orchestrated on the internet and agent behaviors were built in them. Data analysis, model, optimization, control, fault diagnosis and so on were capsuled into different web services. Agents were used for service compositions by negotiation. A prototype system of poly(ethylene terephthalate) process automation was used as the case study to demonstrate the validation of the integration.

In-situ Enhanced Toughening of Poly（ethylene terephthalate）/elastomer Blends via Gamma-Ray Radiation at Presence of Trimethylolpropane Triacrylate

Gamma-ray radiation has always been a convenient and effective way to modify the inter- facial properties in polymer blends. In this work, a small amount of trimethylolpropane triacrylate （TMPTA） was incorporated into poly（ethylene terephthalate） （PET）/random terpolymer elastomer （ST2000） blends by melt-blending. The existence of TMPTA would induce the crosslinking of PET and ST2000 molecular chains at high temperatures of blend- ing, resulting in the improvement in the impact strength but the loss in the tensile strength. When the PET/ST2000 blends were irradiated by gamma-ray radiation, the integrated me- chanical properties could be enhanced significantly at a high absorbed dose. The irradiated sample at a dose of 100 kGy even couldn＇t be broken under the impact test load, and at the same time, has nearly no loss of tensile strength. Based on the analysis of the impact- fractured surface morphologies of the blends, it can be concluded that gamma-ray radiation at high absorbed dose can further in situ enhance the interfacial adhesion by promoting the crosslinking reactions of TMPTA and polymer chains. As a result, the toughness and strength of PET/ST2000 blend could be dramatically improved. This work provides a facial and practical way to the fabrication of polymer blends with high toughness and strength.