活性炭负载钛酸四丁酯催化合成二乙二醇二苯甲酸酯

以活性炭负载钛酸四丁酯为催化剂,正丁醚为带水剂,采用直接酯化法合成二乙二醇二苯甲酸酯(DEDB);运用低温氮气吸附脱附(BET)与电子顺磁共振波谱(ESR)分析对催化剂进行表征,采用IR和1HNMR进行反应产物的表征;探讨原料比、带水剂用量、反应温度等因素对酯化率的影响。确定了活性炭固载钛酸四丁酯催化二乙二醇(DEG)和苯甲酸(BA)酯化的适宜工艺条件为:原料量比n(DEG)∶n(BA)=1∶2,带水剂占苯甲酸质量分数为20%,催化剂占苯甲酸质量分数为1.5%,反应温度200℃,反应时间6 h。催化剂可循环使用3次,具有较好的稳定性。

二乙二醇二间甲基苯甲酸酯增塑剂的合成

以间甲基苯甲酸和二甘醇为原料,钛酸四丁酯为催化剂合成了二乙二醇二间甲基苯甲酸酯.考查了催化剂及其用量、反应温度、原料配比等条件对反应的影响,经过试验确定适宜工艺条件:甲苯为带水剂,催化剂用量为总反应物的0.5%,醇酸摩尔比为1.0∶2.2,回流反应时间4 h,反应回流温度210℃,转化率达93.7%.产品结构分别用IR、NMR进行表征,并对其作为PVC增塑剂的增塑性能进行了初步评价.

乙二醇苯甲酸二酯降解微生物筛选及性能研究

从土壤和废水中筛选出5株乙二醇苯甲酸二酯降解菌,其中菌株C2能有效降解乙二醇苯甲酸二酯。在含有0.5%乙二醇苯甲酸二酯的培养基中此菌株在pH=7.0,30℃条件下,在30天内将乙二醇苯甲酸二酯完全降解。底物特性研究表明菌株C2可以利用多种含有苯环的盐类和酯类为碳源,其中原儿茶酸为单一碳源时,菌株C2生长情况最好,其次为对羟基苯甲酸、苯甲酸和底物乙二醇苯甲酸二酯。对于菌株C2上乙二醇苯甲酸二酯降解酶分布的初步研究表明其降解酶主要分布在细胞表面。

可控微波促进AlCl_3催化下二酯类化合物的环境友好合成

利用可控微波加热技术,在无溶剂条件下,以Lewis酸为催化剂,羧酸与乙二醇、酸酐与一元醇发生双酯化反应,"一锅"法合成了不同类型的二酯类化合物.通过原料比、微波辐射时间、温度、催化剂种类及催化剂用量优化出最佳反应条件.在微波筛选条件的基础上,采用常规放大实验,合成克级二酯产物.产物的结构通过熔点测定、红外光谱分析确定.

“二次白泥”合成DOTP的研究

“二次白泥”是以碱减量白泥为原料生产DOTP过程中,和废水酸析产生的固体物料压滤得到的产物,通过红外光谱以及合成反应实验,确定了二次白泥的主要组成为乙二醇二对羧基苯甲酸酯。以“二次白泥”为原料,通过酯化、醇解反应合成DOTP,考察了醇酸摩尔比、催化剂加入量以及反应终点温度对反应时间和产品收率的影响,实验表明醇酸摩尔比为6.0、催化剂加入量为酸量的0.5%、反应终点温度为225~230℃,反应7.5 h即可合格,收率达93%,产品纯度达99.07%,各项指标均达到电缆料使用标准。

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.

Simultaneous Synthesis of Dimethyl Carbonate and Poly（ethylene terephthalate） Using Alkali Metals as Catalysts

Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.

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.

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.

Properties of Surface Cyclic Oligomers Present on Polyester Fiber

The effects of different treatments, such as dry heat,wet heat, solvent vapor and ultrasonic, on propertiesof the cyclic oligomers on the surface of polyester fiberare studied. The components of surface oligomers areanalyzed through Thin-Layer Chromatograph. Theresult shows that: all of the treatment, especially solvent vapor treatment,call significantly increase the content of surface cyclic oligomers.The content of cyclic triIner is increased more considerably than other oligomers. Moreover,the morphology and thedistribution of surface cyclic oligomers are also different from different treatments:Dry heat and wet heat cause larger polygonal solids distributed evenly on the surface of fiber;solvent vapor nlakes fiber surface exhibit irregular rodlike crystal shapes randomly;ultrasonic treatment induces some obscureand smaller deposi^on the surface of fiber.

Degradation behaviors,thermostability and mechanical properties of poly(ethylene terephthalate)/polylactic acid blends

It is difficult for polyethylene terephthalate （PET） to degrade,which caused severe pollution.In this work,polylactic acid （PLA） was introduced to improve the degradation of PET.PET/PLA was synthesized by extrusion blending.The thermal,crystalline and mechanical properties of blends were investigated with TGA,DSC,WAXD and universal testing machine.The degradation of the blends in soil,acid and alkaline buffer solutions was assessed,respectively.It was found that the introduction of a little PLA promoted crystallization of PET during injection molding process.The starting decomposition temperature lowered from 412.1 ℃ of pure PET to 330.4 ℃ at 50% PLA content,tensile and bending strength of blends gradually decreased with the PLA content increasing,while the degradation rate improved.Alkaline environment was most beneficial for blends to degrade.The degradation mechanism was discussed.

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.

Mechariical and Abrasion Properties of Polyethylene Terephthalate Films Coated with SiO2/Epoxy Hybrid Material

Hybrid materials were prepared using a silane coupling agent, tetraethoxysilane （ TEOS ） as the precursor, dilute hydrochloric acid as the catalyst, and epoxy as the matrices. The films coated with hybrid materials were expected to improve abrasion resistance and mechanical properties. The morphology, mechanical properties, adhesion, and abrasion resistance of the polyethylene terephthalate （PET） films were characterized using an atomic force microscope, a tensile testing machine, a bagger knife, and a reciprocating fabric abrasion tester. The result of research indicated that the modification significantly affected the abrasion resistance and roughness. The-tensile strength and abrasion resistance of the modified PET films increased by 40% and 50% respectively at 3 % TEOS mass fraction.

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.

Dynamics Model and Simulation of Polyethylene Terephthalate (PET) Hollow Fiber

On the basis of melt-spinning, the dynamics model of polyethylene terephthalate （PET） hollow fiber is established. The effects of spinning conditions on hollow ratio are discussed and verified. Because of the different quenching conditions, there exist differences of the hollow ratio and the vitrification distances between different cycles. The important role of the quenching conditions on the meltspinning of PEr hollow fiber is also mentioned.

Study on the Synthesis and Properties of PET Using Hydrotalcite as Catalyst

Poly(ethylene terephthalate)(PET)was synthesized by the in-situ polymerization method using layered double hydrotalcite(LDH)as the catalyst,and the thermal and flame retardation properties of PET were investigated as required.As identified by differential scanning calorimetry(DSC)and thermogravimetric(TGA)analysis,the crystallization rate and thermal degradation temperature of the as-prepared PET sample were enhanced compared with commercial PET sample.It was confirmed from the fire-resistant property study that the LDH can be used as an efficient flame-retardant besides functioning as a catalyst in the transesterification/polycondensation process for PET synthesis.

Nonisothermal Crystallization Kinetics of Poly(phenylene sulfide)/Poly(ethylene-co-cyclohexane 1,4-dimethanol terephthalate) Blend

Binary alloy samples consisting of poly（phenylene sulfide） （PPS）/poly（ethylene terephthalate-co-cyclohexane 1,4-dimethanol terephthalate） （PETG） blend were prepared by the melt blending technology using a twin-screw extruder. The nonisothermal crystallization kinetics of binary alloys made of poly（phenylene sulfide） （PPS） and poly（ethyleneco-cyclohexane 1,4-dimethanol terephthalate） （PETG） was studied by the differential scanning calorimetry （DSC） at different cooling rates. The test results revealed that the addition of PETG could shift the crystallization temperature of PPS toward the high-temperature direction. The nonisothermal crystallization kinetic parameters of the PPS/PETG alloy samples were calculated by the methods proposed by Avrami and Mo. Test results demonstrated that the PPS/PETG alloy could give birth to apparent secondary crystallization. The value of Avrami exponent was lower relatively, while Mo＇s method was more suited to the nonisothermal crystallization process of the PPS/PETG alloy.

Screening of Polymer Additives in Drinking Water Stored in PET Bottles by UHPLC-ESI-IT-TOF MS

In this study, Ultra High Performance Electrospray Ionization Ion Trap Time of Flight Mass Spectrometry （UHPLC-ESI-1T-TOF MS） method is used to screen the polymer additives in drinking water that is stored in Polyethylene Terephthalate （PET） bottles. After directly analyzing the commercially available water samples, 3 polymer additives （chimassorb 81, irgafos 168 and oleamide） were detected. However, after exposure to sunshine for 8 days, two additional polymer additives （antioxidant 2246 and Butylated Hydroxytoluene （BHT）） were detected besides the former three additives.

Solar Oxidation and Removal of Arsenic from Groundwater Utilizing a Semicircular Section Tubular Photoreactor

A semicircular section tubular photoreactor has been constructed, characterized and applied to the treatment of groundwater contaminated with As（V） by means of the SORAS （solar oxidation and removal of arsenic） technique, using ferrous and citrate salts. The solar concentrator was built with recyclable waste materials： glass tubes from fluorescent lamps and 6-inch diameter PVC pipes cut in half and covered by aluminum foil. The reactor concentrates solar radiation up to 2.8 times its natural intensity. Batch irradiation experiments followed by controlled agitation （shear rate = 30-33 s^-1; 20 min agitation period） showed that the photoreactor accelerates the formation of settleable floccules （Dp 〉 0.5mm）, compared with a fluorescent lamp glass tube alone and a 2 L PET （polyethylene terephthalate） bottle. Irradiation times necessary for floccule formation in the photoreactor, the fluorescent lamp tube and the PET bottle were 15 min, 25 min and 60 min, respectively. Continuous flow experiments using a photoreactor with a photo-collection area of 0.9 m^2 and a hydraulic retention time （equal to the irradiation time） of 15 rain showed that immediate formation of floccules of good settleability occurs when the solution is subjected to moderate agitation （33 s^-1）. An efficiency of 98.36% for As（V） removal was obtained with a final concentration of 16.5 ktg/L in decanted waters. In accordance to these results, the photoreactor is able to treat approximately 130 L/m^2 within a 5-h period with UVA irradiation intensities of 50-70 W/mE.

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.