Preparation and characterizations of thermotropic copolyesters of p-hydroxybenzoic acid,sebacic acid,and hydroquinone

A series of copolyesters of p-hydroxybenzoic acid (HBA), sebacic acid and hydroquinone were prepared by melt polycondensation of p-acetoxybenzoic acid, sebacic acid and p-phenylene diacetate. The copolyesters were characterized by IR, NMR, DSC, polarized microscopy, and X-ray diffraction. It was found that the copolyesters exhibited liquid crystallinity when the HBA content was 25–67 mol %. The copolyesters with an HBA content of 25–43 mol % showed a nematic phase and a biphasic range, and the isotropization temperature increased as the HBA content increased. The copolyesters with an HBA content of 54–67 mol % showed a nematic phase up to above 400°C. The liquid crystalline order increased as the HBA content increased due to the increased of the average length of the rigid moieties. © 1995 John Wiley & Sons, Inc.     

功能化聚酯的结构设计、合成及应用

综述了功能化可降解聚酯在分子结构设计、合成方法及应用等方面的最新进展,主要包括功能化聚丙交酯、聚己内酯、聚乙交酯和聚丁二酸丁二醇酯等。同时,对功能化可降解聚酯的发展趋势及潜在应用进行了分析和展望。     

Synthesis and characterization of block copolymers from aromatic diols,fumaric acid,sebacic acid and PEG

The syntheses of two linear unsaturated aromatic oligoesters, poly(hydroquinone fumarate‐co‐sebacate) (PHFS) and poly(resorcinol fumarate‐co‐sebacate) (PRFS), are described. PHFS, PRFS and poly(ethylene glycol) (PEG) are then used to prepare di‐ and tri‐block copolymers. Products thus obtained are investigated in terms of molecular weight, composition, structure and thermal properties by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and NMR and FTIR spectroscopies. A number of design parameters including the molecular weights of PHFS, PRFS and PEG and the ratios of PEG to PPFS or to PEFS are varied in order to assess their effects on product yields and properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2358–2363, 2003     

癸二酸改性PET共聚酯的合成与性能研究

采用癸二酸(SA)、对苯二甲酸(PTA)、乙二醇(EG)进行熔融缩聚反应,合成了不同含量SA改性PET共聚酯,探讨了SA添加量对改性PET共聚酯的聚合过程及常规性能指标的影响,对其拉伸和弯曲性能进行了表征。结果表明:随SA用量的增加,所得改性PET共聚酯的特性黏度逐渐增大,且其端羧基(COOH)、玻璃化转变温度(T_g)、冷结晶峰温度(T_c)、熔融结晶峰温度(T_(mc))和熔点(T_m)等指标均呈下降趋势;拉伸强度变化不大,断裂伸长率逐渐变大;弯曲强度与弯曲模量在SA含量超过5%后呈下降趋势。     

Polyester–Polycarbonate blends. III. Polyesters based on 1,4-cyclohexanedimethanol/terephthalic acid/isophthalic acid

Melt blends of polycarbonate with Kodel, a homopolyester formed from 1,4-cyclohexanedimethanol and terephthalic acid, and with Kodar, a copolyester formed by replacing some of the terephthalic acid with isophthalic acid, were prepared and their transitional behavior were examined by thermal analysis and dynamic mechanical testing. Blends formed with either polyester were found to have a single T_g over the entire compositional range. Single composition-dependent α- and β-relaxation temperatures were also observed for blends made with either polyester at all compositions. From these data it is concluded that both Kodel and Kodar blends with polycarbonate form miscible amorphous phases. The role of ester–carbonate interchange reactions during melt mixing was experimentally examined and found to be unimportant, from which it is concluded that the observed miscible phase formation is due to physical interactions between the blend components.     

Simultaneous determination of catechol and hydroquinone based on poly(sulfosalicylic acid)/functionalized graphene modified electrode

A glassy carbon electrode (GCE) modified with poly(sulfosalicylic acid) (PSA) and poly(diallyldimethylammonium chloride)-graphene (PDDA-GN) was prepared by a simple self-assembly method. The formation of films was ascribed to the electrostatic force between negatively charged PSA and positively charged PDDA-GN as well as the π–π stacking interaction between PSA and PDDA-GN. The as prepared films were characterized by scanning electron microscopy (SEM), Raman spectroscopy and electrochemical methods. Under the optimized condition, the modified GCE showed two well-defined redox waves for catechol (CT) and hydroquinone (HQ) in cyclic voltammetry (CV) with a peak potential separation of 111 mV, which ensured the anti-interference ability of the electrochemical sensor and made simultaneous determination of dihydroxybenzene isomers possible in real samples. The corresponding oxidation currents increased remarkably compared with those obtained at the bare GCE, PSA/GCE and PDDA-GN/GCE, respectively. Differential pulse voltammetry (DPV) was used for the simultaneous determination of CT and HQ. The anodic peak current of CT was linear in the concentration from 1 × 10^?6 to 4 × 10^?4 M in the presence of 3 × 10^?5 M HQ, and the detection limit was 2.2 × 10^?7 M (S/N = 3). At the same time, the anodic peak current of HQ was linear in the concentration from 2 × 10^?6 to 4 × 10^?4 M in the presence of 2 × 10^?5 M CT, and the detection limit was 3.9 × 10^?7 M (S/N = 3). The proposed method was applied to simultaneous determination of CT and HQ in tap water with satisfactory results. These results indicated that PSA/PDDA-GN is a promising modified material with great potential in electrocatalysis and electrochemical sensing.     

Biodegradable polymers based on renewable resources: Polyesters composed of 1,4 : 3,6-dianhydrohexitol and aliphatic dicarboxylic acid units

A series of polyesters was synthesized by the bulk polycondensations of the respective combinations of three stereoisomeric 1,4 : 3,6-dianhydrohexitols [1,4 : 3,6-dianhydro-D-glucitol ( 1 ), 1,4 : 3,6-dianhydro-D-mannitol ( 2 ), and 1,4 : 3,6-dianhydro-L-iditol ( 3 )] with succinyl dichloride ( 4a ), glutaryl dichloride ( 4b ), adipoyl dichloride ( 4c ), and sebacoyl dichloride ( 4d ). Biodegradability of these polyesters was investigated by three different methods, i.e., degradation in an activated sludge, soil burial degradation, and enzymatic degradation. Although polyesters ( 7b–7d ) based on 3 and polyester 6a derived from 2 and 4a were crystalline and scarcely biodegraded, all the other amorphous polyesters were more or less biodegradable. Biodegradability of the polyesters was found to vary significantly depending on their molecular structures. Soil burial degradation of polyesters in the soil that was treated with antibiotics, together with electron scanning microscopic observation, showed that polyesters 5b and 5c prepared from 1 and 4b or 4c were degraded by both bacteria and filamentous fungi, whereas polyester 5d from 1 and 4d was degraded primarily by filamentous fungi. © 1996 John Wiley & Sons, Inc.     

Newer intermediates for plastics and coatings. III. Polyesters based on methylene-di-β-oxynaphthoic acid

A tetrafunctional dibasic acid, methylene-di-β-oxynaphthoic acid (MDNA), has been used for preparation of unsaturated polyester resins. The films obtained from these products have excellent chemical and physical properties comparable to epoxy resins and to a large extent balance some of their shortcomings such as darker color, higher viscosities, and higher cooking temperatures. The possible applications of these resins are coatings where acid, corrosion, and thermal resistance are of primary importance.     

Thermotropic mesomorphic polyesters. I. Copolyesters of terephthalic acid,hydroquinone, and flexible diols

A new series of copolyesters has been synthesized by low-temperature solution polycondensation of terephthaloyl dichloride hydroquinone and flexible diols such as 1,2-propane diol, 1,4-butanediol, diethylene glycol, (cis) 1,4-cyclohexanediol and (cis + trans) 1,4-bis(hydroxymethyl) cyclohexane. The copolyesters are all insoluble and display thermotropic mesophases at relatively lower transitions than other commercially important systems. The transition temperatures, the crystallinity, and thermal characterization are reported.     

Molecular design of photovoltaic materials for polymer solar cells: toward suitable electronic energy levels and broad absorption

Bulk heterojunction (BHJ) polymer solar cells (PSCs) sandwich a blend layer of conjugated polymer donor and fullerene derivative acceptor between a transparent ITO positive electrode and a low work function metal negative electrode. In comparison with traditional inorganic semiconductor solar cells, PSCs offer a simpler device structure, easier fabrication, lower cost, and lighter weight, and these structures can be fabricated into flexible devices. But currently the power conversion efficiency (PCE) of the PSCs is not sufficient for future commercialization. The polymer donors and fullerene derivative acceptors are the key photovoltaic materials that will need to be optimized for high-performance PSCs. In this Account, I discuss the basic requirements and scientific issues in the molecular design of high efficiency photovoltaic molecules. I also summarize recent progress in electronic energy level engineering and absorption spectral broadening of the donor and acceptor photovoltaic materials by my research group and others. For high-efficiency conjugated polymer donors, key requirements are a narrower energy bandgap (E(g)) and broad absorption, relatively lower-lying HOMO (the highest occupied molecular orbital) level, and higher hole mobility. There are three strategies to meet these requirements: D-A copolymerization for narrower E(g) and lower-lying HOMO, substitution with electron-withdrawing groups for lower-lying HOMO, and two-dimensional conjugation for broad absorption and higher hole mobility. Moreover, better main chain planarity and less side chain steric hindrance could strengthen π-π stacking and increase hole mobility. Furthermore, the molecular weight of the polymers also influences their photovoltaic performance. To produce high efficiency photovoltaic polymers, researchers should attempt to increase molecular weight while maintaining solubility. High-efficiency D-A copolymers have been obtained by using benzodithiophene (BDT), dithienosilole (DTS), or indacenodithiophene (IDT) donor unit and benzothiadiazole (BT), thienopyrrole-dione (TPD), or thiazolothiazole (TTz) acceptor units. The BDT unit with two thienyl conjugated side chains is a highly promising unit in constructing high-efficiency copolymer donor materials. The electron-withdrawing groups of ester, ketone, fluorine, or sulfonyl can effectively tune the HOMO energy levels downward. To improve the performance of fullerene derivative acceptors, researchers will need to strengthen absorption in the visible spectrum, upshift the LUMO (the lowest unoccupied molecular orbital) energy level, and increase the electron mobility. [6,6]-Phenyl-C(71)-butyric acid methyl ester (PC(70)BM) is superior to [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) because C(70) absorbs visible light more efficiently. Indene-C(60) bisadduct (ICBA) and Indene-C(70) bisadduct (IC(70)BA) show 0.17 and 0.19 eV higher LUMO energy levels, respectively, than PCBM, due to the electron-rich character of indene and the effect of bisadduct. ICBA and IC(70)BA are excellent acceptors for the P3HT-based PSCs.     

Synthesis,characterization, and hydrolytic degradation of copolyesters of 3‐(4‐hydroxyphenyl) propionic acid and p‐hydroxybenzoic acid,vanilic acid,or syringic acid

A series of copolyesters were prepared by a direct polycondensation of 3‐(4‐hydroxyphenyl) propionic acid and p‐hydroxybenzoic acid (HBA), vanilic acid (VA), or syringic acid (SGA) of different composition in pyridine using diphenyl chlorophosphate and lithium bromide as condensing agents. The effects of methoxy substitution in the benzene ring and copolymer composition on the synthesis and thermal properties as well as hydrolytic degradation were examined. The methoxy substitution increased a glass transition temperature and a solubility, while it decreased a crystallinity and a thermal stability. The HBA series copolyesters showed a homogenous nematic phase, while the VA and SGA series copolyestes neither revealed an anisotropic melt nor formed a mobile melt below around 350°C. The hydrolytic degradation of melt‐pressed films was performed in a 5% sodium hydroxide aqueous solution at 40°C to test a biodegradability of the copolyesters. HBA‐50 and HBA‐30 exhibited the much higher degradation rate than HBA‐70, showing that the aliphatic ester linkage was more degradable than aromatic one. The degradation rates of VA‐50 and SGA‐50 were remarkably slower than that of HBA‐50 due to the steric hindrance of the methoxy group in the ortho position. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2474–2481, 2000     

Liquid crystalline aromatic polyesters formed with terephthalic acid,phenyl hydroquinone,and napthalene or anthracene diols

The synthesis and characterization of aromatic copolyesters containing terephthalic acid and phenyl hydroquinone as the major constituents and either 1,4-napthalene diol or 1,4-anthracene diol as the minority comonomer is described. Both polymers melted in the vicinity of 300°C, giving birefringent fluids. Optical microscopy showed Schlieren textures consisting predominantly of inversion walls characteristic of the nematic phase. The clearing temperature was in the vicinity of 460°C, but was accompanied by charring. DSC experiments showed a high glass transition temperature of 130–160°C for both polymers. Crystalnematic and nematic-isotropic endotherms were observed on heating; however, degradation took place near the isotropization temperature. Thus, on cooling, the sequence was reversible only if the previous heating was beyond the crystal-nematic but below the isotropization temperature. The polymers were stable in terms of gross weight loss until about 450°C, though there were indications that crosslinking occurred above about 400°C over a short period of time. The polymers formed low-viscosity injection-molding compounds, but to use them effectively, it would require mold-gate designs that reduce the “jetting” tendency for liquid crystal polymer melts, which result in weld lines. © 1995 John Wiley & Sons, Inc.     

Molecular design of damping rubber based on polyacrylate‐containing silicone

A series of damping rubbers based on poly(meth)acrylate and poly(meth)acrylate‐containing silicone rubbers has been prepared. The dynamical mechanical properties were evaluated by using a dynamic mechanical viscoelastometer (DMA). A detailed investigation is reported on the relationship of the damping capability of the poly(meth)acrylate rubbers with their composition and macromolecular architecture. Also discussed is the effect of two kinds of silicone elastomers on the damping performance of the polyacrylate‐containing silicone rubber. The results indicate that, in vulcanized rubber systems, both statistical copolymerization for multiple monomers and blending between immiscible polymers with close T_gs facilitate broadening the glass transition peaks. Furthermore, the molecular design is quite an effective approach in which the multiple monomers whose polymers have a ladder‐changing T_g are used to synthesize the damping rubber with the broad effective functional area. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 746–751, 2002     

Synthesis, crystal structure and photoelectric property of two novel coordinated complexes constructed by 4,4′-bipyridine and sebacic acid

Two two-dimensional (2D) new complexes: [M(bpy)(C₁₀H₁₆O₄)H₂O] [M = Ni (1), Co (2); bpy = 4,4-bipyridine, C₁₀H₁₈O₄ = sebacic acid] were synthesized by the hydrothermal reaction at 180 °C and characterized by elemental analysis, infrared spectra, and thermogravimetric spectra, single-crystal X-ray diffraction and surface photovoltage spectrum (SPS). The single-crystal X-ray diffraction showed that both complexes are isomorphous, crystallized in monoclinic system, and space group P2₁/c. In addition, The results of SPS for complexes (1) and (2) indicate that these two complexes exhibit positive surface photovoltage response in the range of 300–800 nm, which can be assigned to LMCT and d → d^* electronic transition. The SPS spectra of the two complexes are consistent with their UV–Vis spectra.     

Biodegradable Polyesters and Low Molecular Weight Polyethylene in Soil: Interrelations of Material Properties,Soil Organic Matter Substances,and Microbial Community

Conventional and also biodegradable polymer microplastics have started to be broadly present in the environment, if they end up in soil, they may influence both abiotic and biotic soil properties. In this study, the interactions of polyethylene wax together with three biodegradable polyesters PLA, PHB and PBAT with a soil matrix were investigated over a 1-year incubation period. Soil organic matter content was measured using UV–VIS, the microbial biomass amount was measured using qPCR, the mineralisation of polymers was measured using UGA 3000, the surface of polymers was observed with SEM, live/dead microorganisms were determined by fluorescent microscopy and microbial consortia diversity was analyzed using NGS. The amount of humic substances was generally higher in incubations with slowly degrading polyesters, but the effect was temporary. The microbial biomass grew during the incubations; the addition of PHB enhanced fungal biomass whereas PE wax enhanced bacterial biomass. Fungal microbial consortia diversity was altered in incubations with PHB and PBAT. Interestingly, these two polyesters were also covered in biofilm, probably fungal. No such trend was observed in a metagenomic analysis of bacteria, although, bacterial biofilm was probably formed on the PE520 surface. Different methods confirmed the effect of certain polymers on the soil environment.     

400 kt/a硫酸亚铁和硫磺、硫铁矿混合制酸工程设计

针对硫酸法钛白粉生产中排出的w（H2SO4）20％硫酸和硫酸亚铁,提出一种以焙烧硫酸亚铁、硫磺和硫铁矿生产硫酸的新工艺.重点介绍了焙烧硫酸亚铁制酸的工艺特点、工程难点及主要设备.焙烧硫酸亚铁制酸装置的成功运行从根本上解决了困扰硫酸法钛白粉生产工艺的废渣及副产物问题,使硫酸法钛白粉生产装置大型化得以实现.     

Molecular design of interfacial layers based on conjugated polythiophenes for polymer and hybrid solar cells

In the past two decades, bulk heterojunction organic photovoltaic (OPV) devices have emerged as attractive candidates for solar energy conversion due to their lightweight design and potential for low‐cost, high‐throughput, solution‐phase processability. Interfacial engineering is a proven efficient approach to achieve OPV devices with high power conversion efficiencies. This mini‐review provides an overview of the key structural considerations necessary when undertaking the molecular design of conjugated polyelectrolytes, for application as interfacial layers (ILs). The different roles of ILs are outlined, together with the advantages and disadvantages of competing classes of IL materials. Particular emphasis is placed on the design and synthesis of water‐soluble polythiophene‐based IL materials and the influence of their structural characteristics on their performance as a promising class of IL material. Finally, the challenges and opportunities for polythiophenes as IL materials for OPV devices and other solution‐processed solar cell technologies (e.g. perovskite solar cells) are discussed. © 2017 Society of Chemical Industry     

正交设计在合成玉米淀粉接枝丙烯酸共聚物中的应用

以过硫酸铵为引发剂,N,N’-亚甲基双丙烯酰胺为交联剂,在玉米淀粉上接枝丙烯酸制备高吸水性树脂。用正交实验,采用L16(45)正交表,考察了丙烯酸的中和度、淀粉与单体比例、引发剂、交联剂等对高吸水性树脂吸水率的影响。制得的树脂吸纯水率可达1 300 g/g,吸质量分数为0.9%NaCl溶液90倍,有较好的热稳定性。     

大冶转炉烟气制酸装置运行总结及设计评述

大冶有色金属有限公司冶炼厂270 kt／a硫酸生产装置净化工序采用两级动力波洗涤的稀酸洗净化工艺,配置两级玻璃钢电除雾器;干吸工序采用低位高效工艺;转化工序采用ⅣⅠ-ⅢⅡ“3 1”两次转化工艺。运行两年多来,主要设备运转正常,性能稳定,系统开车率高,主要技术经济指标经考核达到设计要求,成品硫酸质量达到优等品标准;SO2转化率和SO3吸收率分别达到99．65％和99．99％;外排尾气近乎透明,SO3和SO2含量很低,均优于设计标准和国家标准。     

Preparation,characterization, and adsorption performance of p‐hydroxybenzoic acid imprinted polymer and selective catalysis of toluene to para‐chlorotoluene

A p‐hydroxybenzoic acid surface molecularly imprinted polymer (p‐HB– S MIP) with si lica microspheres as a supporting matrix was prepared by the adoption of the surface molecular imprinting technique with acrylamide ( AM) as a functional monomer, ethylene glycol dimethacrylate as a crosslinker, and azoisobutyronitrile as an initiator. The p‐HB–SMIP was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetry. Interactions between the functional monomer and template were observed with UV–visible spectroscopy of the solutions of these components as well. The results indicate that a 1:2 molecular complex was formed between p‐hydroxybenzoic acid (p‐HB) and AM. A kinetic binding study showed that p‐HB–SMIP reached saturation adsorption after about 1 h, and the pseudo‐second‐order model fitted the adsorption kinetics data. Static adsorption experiments revealed that the Freundlich equation fitted the adsorption isotherm data. The thermodynamics parameters (with positive values of enthalpy and entropy and negative values of Gibbs free energy) indicated that the binding system for p‐HB–SMIP was endothermic and entropy was gained and was spontaneous. Selective experiments showed that p‐HB–SMIP had a high affinity and excellent recognition selectivity for the template p‐HB. p‐HB–SMIP was further investigated by the catalysis of toluene to para‐chlorotoluene. The catalytic reaction results showed that the conversion of toluene was 85.5% and the molar ratio of para‐chlorotoluene to o‐chorotoluene was 1.38; this was higher than that of traditional catalysts. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40118.