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 CO2 pressure 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 35 μm to 49 μm for PENTA modified PETs and 38 μm to 57 μm for PMDA modified ones. Correspondingly, the cell density had a range of 3.5×107cells·cm 3to 7×106 cells·cm 3for the former and 2.8×107cells·cm 3to 5.8×106cells·cm 3for the latter.     

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%.     

Kinetics of Phase Separation in Poly(ɛ-caprolactone)/Poly(ethylene glycol) Blends

The poly(ɛ-caprolactone)/poly(ethylene glycol) (PCL/PEG) blends reveal a miscibility window of upper critical solution temperature (UCST) character. The kinetics of liquid–liquid phase separation (LLPS) for the blends of PCL/PEG is investigated by time-resolved small angle light scattering (TRSALS). The time evolution of scattering profile is analyzed by linear Cahn–Hilliard theory for early stage of spinodal decomposition (SD). The evolution of the maximum intensity I_m(t) and the corresponding wavenumber q_m(t) obey the power-law scheme (I_m(t)∼t^β and q_m(t)∼t^−α). A relation of β=3α in late stage is obtained almost the same scaling exponents with β≅1 and α≅1/3 for various quenching depths. The α≅1/3 implied that a coarsening mechanism at the late stage of phase separation may proceed with Ostwald ripening or Brownian coalescence process. Besides, the intermediate and late stages of SD can be scaled into a universal from represented well by Furukawa’s structure factor. The percolation to cluster transition is accompanied with α∼0.13→1/3 from intermediate to late stage of SD for the off-critical mixture of PCL/PEG (4/6) blend. In this study, the experimental result demonstrates that the crystallization is a viable mechanism to lock phase-separated structure of the blends. The competition between phase separation and crystallization has been suggested to determine the final morphology.     

Modelling of poly(ethylene terephthalate) in injection stretch–blow moulding

Abstract

Simulations of the injection stretch–blow moulding process have been developed for the manufacture of poly(ethylene terephthalate) bottles using the commercial finite element package ABAQUS/standard. Initially a simulation of the manufacture of a 330 mL bottle was developed with three different material models (hyperelastic, creep, and a non-linear viscoelastic model (Buckley model)) to ascertain their suitability for modelling poly(ethylene terephthalate). The Buckley model was found to give results for the sidewall thickness that matched best with those measured from bottles off the production line. Following the investigation of the material models, the Buckley model was chosen to conduct a three-dimensional simulation of the manufacture of a 2 L bottle. It was found that the model was also capable of predicting the wall thickness distribution accurately for this bottle. In the development of the three-dimensional simulation a novel approach, which uses an axisymmetric model until the material reaches the petaloid base, was developed. This resulted in substantial savings in computing time.     

Production of Poly（3-Hydroxybutyrate） by Fed-Batch Culture of Alcaligenes Eutrophus at Phosphorus Limitation in 50L fermenter

1 INTRODUCTIONPoly(3-hydroxybutyrate)(PHB)is an intracellular carbon and energy storage material accumu-lated by many kinds of microorganism under unfavorable growth conditions such as limitation of(NH_4)_2SO_4,PO_3~(2-),Mg~(2 ) and /or oxygen~(1-3).PHB is a biodegradable thermoplastic polyesterwhich can be used as similar as the conventional nondegradable plastics in various ways.Al-caligenes eutrophus has been widely used for the production of PHB because it is easy to grow,     

Study on Synthesis and Chloramphenicol Release of Poly（2-hydroxyethylmethacrylate-co-acrylamide） Hydrogels

In this article, poly（2-hydroxyethylmethacrylate-co-acrylamide） hydrogels were synthesized by bulk free-radical copolymerization of 2-hydroxyethylmethacrylate （HEMA） and acrylamide （AAm） for soft contact lens（SCL）-based ophthalmic drug delivery system. The copolymer was characterized with FT-IR and SEM, the swelling property of the hydrogels were studied by gravimetrical method, and chloramphenicol was used as a model drug to investigate drug release profile of the hydrogels. The results showed that poly（2-hydroxyethylmethacrylateco-acrylamide） hydrogels were transparent and useful SCL biomaterial, the water content increased as AAm content increase and pH decrease, and in the same way, hydrogel composition affected chloramphenicol release process too. Migration rate of chloramphenicol increased as the AAm content in the hydrogels increased in the first stage of diffusion process, whereas there was no significant difference thereafter.     

Fabrication of Poly（y-glutamic acid）-coated Fe3O4 Magnetic Nanoparticles and Their Application in Heavy Metal Removal

In this study, poly（y-glutamic acid）-coated Fe3O4 magnetic nanoparticles （y-PGA/Fe304 MNPs） were successfully fabricated using the co-precipitation method. Fe3O4 MNPs were also prepared for comparison. The av erage size and specific surface area results reveal that 7-PGA/Fe304 MNPs （52.4 nm, 88.41 m2.g-1） have smaller particle size and larger specific surface area_ than Fe3O4 MNPs （62.0 nm, 76.83 mLg-1）. The y-PGA/Fe3O4 MNPs     

化工（甲醇）贮罐制作优化设计浅谈

0 前言 江苏恒盛化肥有限公司从2007年末起,在工业园区新增“18·30”装置及200kt／a低压甲醇装置各1套。笔者主要负责低压甲醇系统的甲醇贮罐（6个3000m^3储罐,8个240m^3贮罐）制作和安装项目,其设计的好坏关系到贮罐的安全可靠性以及今后维修和工程造价的问题。在设计中必须考虑贮罐的强度、刚度、稳定性和防腐措施,同时合理地选择设计参数及贮罐的结构形式,并且尽可能地节省钢材,力争优化设计。     

Phase Transition Behavior and Electrical Properties of （1-x）K（0.5）Na（0.5）NbO3-xCa（0.3）Ba（0.7）TiO3 Lead-Free Piezoelectric Ceramics

采用固相法制备了（1–x）K0.5Na0.5NbO3–xCa0.3Ba0.7TiO3[（1–x）KNN–xCBT]系列无铅压电陶瓷,研究了CBT的含量（x=0～0.08）对样品的物相结构、显微形貌、介电性能以及压电性能的影响。结果表明：所有样品都具有钙钛矿结构;随着x的增加,室温下样品从正交相逐渐向四方相过渡并且Curie温度向低温方向移动,样品的压电常数d33与机电耦合系数kp均先升高后降低。（1–x）KNN–xCBT多晶型转变位于0.03≤x≤0.04,当x=0.03时,样品的压电性能达到最佳：d33=142 pC/N,kp=40%,其介电损耗tanδ从室温到380℃范围内几乎不变且小于0.05,表明组分为x=0.03的陶瓷是一种非常有前景的无铅压电材料。     

Depolymerization of poly(butylene terephthalate) using high‐temperature and high‐pressure methanol

Poly(butylene terephthalate) (PBT) was depolymerized in excess methanol at high‐temperature (473–523 K) and high‐pressure (4–14 MPa) conditions. Considering the critical point of methanol (512.6 K, 8.09 MPa), the reaction pressure was varied over the range of 6–14 MPa at the reaction temperature of 513 K. As a result, ca. 20 min was required to recover dimethyl terephthalate and 1,4‐butanediol, quantitatively, at any pressure, indicating that the supercritical state of methanol is not a key factor of degradation of PBT and that the effect of pressure is little. On the contrary, when the reaction temperature was varied over the range of 473–523 K at the pressure 12 MPa, the decomposition rate constant of PBT at the reaction temperatures (503–523 K) higher than the melting temperature of PBT (500 K) was much higher than that at 473–483 K. This result indicates that melting of PBT is an important factor for the short‐time depolymerization of PBT. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3228–3233, 2000     

双酚A型氰酸酯的三聚体对PET扩链的影响

使用双酚A型氰酸酯(BADCy)的三聚体Tri-mer-60作为扩链剂,与BADCy单体进行对比,对聚苯二甲酸乙二醇酯(PET)进行扩链.通过比较扩链后的PET的熔体扭矩,发现三聚体对PET的扩链效果优于单体.并研究了不同含量的Tri-mer-60对PET的扭矩、特性黏度、羧基含量、流变性能以及结晶性能的影响.结果表明:随着Tri-mer-60含量的增加,扩链反应速度增加,PET的特性黏度增加,羧基含量降低.扩链反应的发生改善了PET的流变性能,但阻碍了PET的结晶.     

Chemical Recycling of Poly(ethylene terephthalate)

This paper covers the recent research carried out by the authors on the chemical recycling of poly(ethylene terephthalate) (PET) taken from post‐consumer soft‐drink bottles. The chemical recycling techniques used are critically reviewed and the authors' contribution is highlighted. Hydrolysis in either an alkaline or acid environment was employed in order to recover pure terephthalic acid monomer that could be repolymerized to form the polymer again. Alkaline hydrolysis was carried out in either an aqueous NaOH solution or in a non‐aqueous solution of KOH in methyl cellosolve. A phase‐transfer catalyst was introduced in alkaline hydrolysis, in order that the reaction takes place at atmospheric pressure and in mild experimental conditions. The reaction kinetics were thoroughly investigated, both experimentally and theoretically, using a simple, yet precise, kinetic model. Moreover, glycolysis was examined as an effective way for the production of secondary value‐added materials. The glycolysated PET products (oligomers) can be used as raw materials for the production of either unsaturated polyester resins (UPR) or methacrylated oligoesters (MO). UPR can subsequently be cured with styrene in ambient temperature to produce alkyd resins used as enamel paints or coatings. MO are potential monomers that can be cured either by UV irradiation or temperature to produce formulations used as coatings for wood surfaces, paints, or other applications. Thus, recycling of PET does not only serve as a partial solution to the solid‐waste problem, but also contributes to the conservation of raw petrochemical products and energy.

     

Glycolysis of poly(ethylene terephthalate) wastes in xylene

To reclaim the monomers or prepare intermediates suitable for other polymers zinc acetate catalayzed glycolysis of waste poly(ethylene terephthalate) (PET) was carried out with ethylene or propylene glycol, with PET/glycol molar ratios of1 : 0.5–1 : 3, in xylene at 170–245°C. During the multiphase reaction, depolymerization products transferred to the xylene medium from the dispersed PET/glycol droplets, shifting the equilibrium to glycolysis. Best results were obtained from the ethylene glycol (EG) reaction at 220°C, which yielded 80 mol % bis-2-hydroxyethyl terephthalate monomer and 20 mol % dimer fractions in quite pure crystalline form. Other advantages of employment of xylene in glycolysis of PET were improvement of mixing at high PET/EG ratios and recycling possibility of excess glycol, which separates from the xylene phase at low temperatures. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2311–2319, 1998     

Kinetic and thermodynamic study of methanolysis of poly(ethylene terephthalate) waste powder

Depolymerization of poly(ethylene terephthalate) waste (PETW) was carried out by methanolysis using zinc acetate in the presence of lead acetate as the catalyst at 120–140 °C in a closed batch reactor. The particle size ranging from 50 to 512.5 µm and the reaction time 60 to 150 min required for methanolysis of PETW were optimized. Optimal percentage conversion of PETW into dimethyl terephthalate (DMT) and ethylene glycol (EG) was 97.8% (at 120 °C) and 100% (at 130 and 140 °C) for the optimal reaction time of 120 min. Yields of DMT and EG were almost equal to PET conversion. EG and DMT were analyzed qualitatively and quantitatively. To avoid oxidation/carbonization during the reaction, methanolysis reactions were carried out below 150 °C. A kinetic model is developed and the experimental data show good agreement with the kinetic model. Rate constants, equilibrium constant, Gibbs free energy, enthalpy and entropy of reaction are also evaluated at 120, 130 and 140 °C. The methanolysis rate constant of the reaction at 140 °C (10.3 atm) was 1.4 × 10^?3 g PET mol^?1 min^?1. The activation energy and the frequency factor for methanolysis of PETW were 95.31 kJ mol^?1 and 107.1 g PET mol^?1 min^?1, respectively. © 2003 Society of Chemical Industry     

Depolymerization of poly(ethylene terephthalate) wastes using ethanol and ethanol/water in supercritical conditions

Chemical recycling of poly(ethylene terephthalate) (PET) in supercritical ethanol has been investigated. In the presence of water, under supercritical conditions (temperature and pressure above 516 K and 6,384 kPa, respectively) excess ethanol reacts with PET to form diethyl terephthalate (DET) as the main product. A laboratory‐made 0.1 L ‐batch reactor was used at 528 K under pressures from 7,600 and 11,600 kPa. After the required reaction times, the reaction products were analyzed by reverse phase high pressure liquid chromatography and nuclear magnetic resonance. It was found that PET is completely depolymerized into monomers in about 5 h. The influences of water, pressure, ethanol/PET weight ratio, PET sources, as well as depolymerization time were investigated. Maximum DET recovery yield was 98.5%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2009–2016, 2006     

Alkali decomposition of poly(ethylene terephthalate) with sodium hydroxide in nonaqueous ethylene glycol: A study on recycling of terephthalic acid and ethylene glycol

Pellets of poly(ethylene terephthalate) (PET; 0.48–1.92 g) were heated in anhydrous ethylene glycol (EG; 5 mL) with 2-equivs of NaOH at 150°C for 80 min or 180°C for 15 min to convert them quantitatively to disodium terephthalate (Na₂-TPA) and EG. The disodium salt was precipitated quantitatively in pure state from the EG solution and separated readily. The other product EG, being the same component to the solvent, remains in the solution and can be obtained after distillation as a part of the solvent. The rate of decomposition was significantly accelerated by the addition of ethereal solvents to EG, such as dioxane, tetrahydrofuran, and dimethoxyethane. The reaction system is simple; no water and no extra reagent other than NaOH and EG are used. A few recycling systems of PET can be designed on the basis of the present alkali decomposition reaction. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 595–601, 1997     

Depolymerization of poly(trimethylene terephthalate) in supercritical methanol

The depolymerization of poly(trimethylene terephthalate) (PTT) in supercritical methanol was carried out with a batch‐type autoclave reactor at temperatures ranging from 280 to 340°C, at pressures ranging from 2.0 to 14.0 MPa, and for reaction time of up to 60 min. PTT quantitatively decomposed into dimethyl terephthalate (DMT) and 1,3‐propaniol (PDO) under the designed conditions. The yields of DMT and PDO greatly increased as the temperature rose. The yields of the monomers markedly increased as the pressure increased to 10.0 MPa, and they leveled off at higher pressures. The final yield of DMT at 320°C and 10.0 MPa reached 98.2%, which was much closer to the extent of the complete reaction. A kinetic model was used to describe the depolymerization reaction, and it fit the experimental data well. The dependence of the forward rate constant on the reaction temperature was correlated with an Arrhenius plot, which gave an activation energy of 56.8 kJ/mol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2363–2368, 2004     

Surface analyses of corona-treated poly(ethylene terephthalate)

Poly(ethylene terephthalate) (PET) Mylar® samples were treated by corona discharge in order to improve their adhesive properties. The corona treatments were performed in different atmospheres including nitrogen, ammonia and air. X-ray photoelectron spectroscopy (XPS) was used to investigate the chemical modifications induced at the PET surface by these corona treatments. XPS results show that nitrogen incorporation takes place in the form of non-oxygenated nitrogen functionalities, like amine or cyano groups. These are present at the surface of all the corona-treated samples but in different concentrations depending on the gases used in the corona discharge. Furthermore, XPS analyses performed after heating of the treated samples show a higher thermal stability of the corona-induced surface modifications in the case of nitrogen and ammonia. Ion scattering spectroscopy (ISS) and static secondary ion mass spectroscopy (SIMS) analyses were also performed because of their higher surface sensitivity compared with XPS: ISS reveals that nitrogen is not present at the topmost surface layer of the treated samples but is incorporated just beneath. The outermost surface layer presents a composition rich in oxygen. Finally, static SIMS spectra show that corona treatment induces more surface degradation when performed in air compared with nitrogen or ammonia. These results are discussed in relation to adhesive properties of PET.     

Recyclability of In Situ Microfibrillar Poly(ethylene terephthalate)/High‐Density Polyethylene Blends

Repetitive processing was employed to assess the recyclability of in situ microfibrillar poly(ethylene terephthalate) (PET)/high‐density polyethylene (HDPE) blends which were fabricated through a “rectangular slit die extrusion–hot stretching–quenching” process. For comparison, the conventional PET/HDPE blends were also obtained using the same processing operation but without hot stretching. The morphological observation indicated that slit die extrusion and hot stretching successfully made the dispersed PET phase deform in situ into well‐defined microfibrils. The average diameter of the microfibrils increased with the processing cycles. The rheological properties obtained from the parallel‐plate dynamic rheometer suggested that the microfibrillar blends have higher viscosity and viscoelastic moduli (storage and loss moduli) as well as better flow stability than the conventional PET/HDPE blend. More importantly, with the increase in the processing cycles, an increase in yield strength and unchanged tensile modulus were observed for in situ microfibrillar blends, while a decrease in these properties for conventional blend, indicating that the in situ microfibrillar PET/HDPE blends have promising recycling potential.