Graft copolymerization of styrene and acrylonitrile onto EPDM

Acrylonitrile–EPDM–styrene (AES) graft copolymers were synthesized by solution graft polymerization of styrene (St) and acrylonitrile (AN) onto EPDM in an n‐hexane/benzene solvent with benzoyl peroxide (BPO) as an initiator. The structure changes were studied by an FTIR spectrophotometer. The grafting parameters were calculated gravimetrically. The influence of the polymerization conditions, such as the reaction time, concentration of the initiator, EPDM content, and weight ratio of St/AN, on the structure of the products was investigated. It was found that a proper initiator concentration and EPDM content will give a high grafting ratio of the AES resin. The thermal property of the copolymer was studied using programmed thermogravimetric analysis (TGA). The results showed that the copolymer has a better heat‐resistant property than that of ABS, especially for the initial decomposition temperature (T_in) and the maximum weight loss rate temperature (T_max). Also, the mechanism of the graft reaction was discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 428–432, 2002     

一步法合成硫化剂双25的新方法

报道一种有机过氧化物 2 ,5 -二甲基 -2 ,5 -双 (叔丁过氧基 )己烷 (简称双 2 5 )的合成新方法。研究了反应温度、过氧化氢浓度、反应物摩尔比以及反应物加入顺序对产品产率、品质的影响。该双2 5与硅橡胶硫化后的混炼胶物经各种性能测试 ,结果表明具有优良的性能     

Change of the amorphous state by heat treatment below the glass transition temperature

This study was undertaken to elucidate the state of a polymer in the amorphous state through a change of motion of the molecular chain caused by heat treatment below the glass transition temperature. From dielectric measurements of amorphous poly(ethylene terephthalate) heat-treated below T_g, it was found that the average relaxation time, the distribution of relaxation time and the dielectric strength increase with increase of heat treatment. From these results, it was concluded that the amorphous state becomes more random by heat treatment.     

PTT／PP／PP-g-MAH共混材料的形态与性能研究

研究了马来酸酐接枝聚丙烯(PP-g-MAH)对聚对苯二甲酸丙二酯(PTT)/聚丙烯(PP)共混体系的形态结构和性能的影响。结果表明,PP在PTT连续相中分散均匀,粒子尺寸随着增容剂含量的增加而细化,分散相与连续相之间有较好的黏结作用,PP-g-MAH改善了PP与PTT的相容性。共混物熔体为假塑性流体,其假塑性随PP-g-MAH含量的增加而升高,熔体表观黏度从1．31 Pa·s降低到1．19 Pa·s,黏流活化能从64．5 kJ/mol降低到36．7 kJ/mol。共混物中PTT和PP可分别结晶,但结晶行为相互影响,PP-g-MAH促进了PTT在高温结晶。共混物的冲击强度随着PP-g-MAH含量的增加从14．2 kJ/m~2提高到33．5 kJ/m~2,拉伸强度在PP-g-MAH含量为5％～10％(质量分数,下同)时最大。共混物的热稳定性随着PP-g-MAH含量的增加而逐渐降低。     

六芳基二咪唑的合成研究

为开发六芳基二咪唑类光致变色材料 ,以联苯甲酰、对甲氧基苯甲醛及乙酸铵为原料 ,经过环合、氧化合成了光致变色化合物 2 ,2′-二对甲氧苯基 - 4,4′,5 ,5′-四苯基 - 1 ,2′-二咪唑。研究了多种因素对反应收率的影响 ,得到最佳工艺条件 :在冰乙酸中 ,联苯甲酰、对甲氧基苯甲醛及醋酸铵物质的量之比为 1∶ 1∶ 8,回流 3 h后生成 2 -对甲氧苯基 - 4,5 -二苯基咪唑 ,收率为 93 .6 % ;以乙二醇 -乙醚为溶剂 ,2 -对甲氧苯基 - 4,5 -二苯基咪唑与氧化剂 K3 [Fe(CN) 6]的物质的量之比为 1∶ 2 ,在 0～1 5°C下反应 5 h,得到产品 2 ,2′-二对甲氧苯基 - 4,4′,5 ,5′-四苯基 - 1 ,2′-二咪唑 ,收率为 87.5 %。     

Electrochemistry at capped platinum nanoparticle Langmuir Blodgett films: A study of the influence of platinum amount and of number of LB layers

Platinum nanoparticles (n-Pt), over-grafted with 2-thiophenecarbonyl chloride are assembled on gold electrodes, by the Langmuir Blodgett (LB) technique using behenic acid (BHA) as promoting agent. These layers are electrochemically active without any preliminary activation. The [Fe(CN)₆]^3−/4− redox couple was used as electrochemical probe. This paper reports on the influence of the number of deposited LB layers, and the n-Pt density on the electrochemical response. n-Pt density was modified by the change of the “BHA/n-Pt” ratio. Cyclic voltammograms of “[Fe(CN)₆]^3−/4−” were observed whatever the coating conditions. As soon as the first layer was deposited the electrochemical response was associated to the n-Pt coverage, its response slightly increased up to a steady state for five or seven layers. As expected, the increase of the Pt density favored the increase of the current density. XPS analysis performed before and after electrochemical cycling showed that 4-mercaptoaniline capped platinum nanoparticles, and their over grafting were chemically and electrochemically stable. Analysis of influence of the number or the n-Pt density of the layers showed that the electrochemically active part of LB electrodes was provided by the last layer plus a part of the underlying one.     

D.s.c. investigation of the states of water in poly(vinyl alcohol-co-itaconic acid) membranes

The state of water in water-swollen poly(vinyl alcohol-co-itaconic acid) membranes, having various water contents from 0.31 to 0.83, was investigated by d.s.c. measurements and compared with those in water-swollen poly(vinyl alcohol) membranes. The amount of freezing water in the membranes was estimated by use of a relationship between the phase transition temperature and the enthalpy of the crystallization of supercooled water. The melting temperature of the water in the membranes immersed in urea and NaCl 0–2 mol l^?1 aqueous solutions was also determined by d.s.c. analysis. The present study proposes a method for estimating the solubilities of urea and NaCl in both of the freezing and the non-freezing water using the melting point depression of the freezing water in the membranes immersed in the solute solution.     

Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 × 10⁻¹⁰ mol cm⁻² and a thickness of 13 Å, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water.     

Structure and conductivity of multi-walled carbon nanotube/poly(3-hexylthiophene) composite films

This work reports a structure-property investigation of a conjugated polymer nanocomposite with enhanced conductivity. Regioregular poly(3-hexylthiophene) (rrP3HT) was used to prepare composites with thin, short, multi-walled carbon nanotube (MWNT) addition over a wide range of concentrations. Scanning and transmission electron microscopies demonstrated an excellent dispersion and good wetting properties within the carbon nanotube composites. Coated MWNTs showed superstructures of P3HT self-organized on nanotube surfaces. Changes in the long range order and on the self-ordered mesophase of the bulk material were investigated by infrared and Raman spectroscopies, differential scanning calorimetry and X-ray diffraction. Interplay between charge transport through the semiconducting polymer and carbon nanotube network increased the composite's conductivity after percolation to values close to 10⁻² S cm⁻¹.     

Preparation and characterization of polypropylene/layered silicate nanocomposites using an antioxidant

Polypropylene (PP)/layered silicate nanocomposites were prepared via simple melt mixing of three components, PP, layered silicates modified with octadecylamine (C18-MMT) and antioxidant, to investigate the role of antioxidant. TEM and X-ray scattering results confirmed the intercalated state of silicates in PP/layered silicate nanocomposites with antioxidant. In rheological and mechanical study, the nanocomposites with antioxidant showed higher properties than those of the unfilled PP. The nanocomposite with 5 wt% C18-MMT and 0.5 phr antioxidant exhibited about 1.4 times higher tensile modulus and 1.3 times higher storage modulus than the unfilled PP. However, PP/C18-MMT without antioxidant showed lower rheological values owing to the thermal decomposition of PP and the poor compatibility between PP and C18-MMT. It could be concluded that antioxidants played an important role in enhancing the compatibility between PP and C18-MMT. According to the real time X-ray diffraction, the nanocomposite showed the weak ordering of PP crystals than the unfilled PP in the load-extension plateau region of elongation.