The thermal degradation of poly(vinyl acetate) and poly(ethylene-co-vinyl acetate), Part I: Experimental study of the degradation mechanism

The thermal degradation mechanism of poly(vinyl acetate) (PVAc) and poly(ethylene-co-vinyl acetate) (EVA) copolymers was investigated with solid-state NMR, thermogravimetry coupled with mass spectrometry and differential thermal analysis. Between 300 and 400 °C acetic acid is eliminated (deacetylation), leaving a highly unsaturated residue or polyene. The deacetylation of PVAc is autocatalytic. Upon incorporation of ethylene entities into the polymer backbone, autocatalysis disappears. Between 400 and 500 °C, the polyene will degrade further by chain scission reactions in inert conditions or aromatise in an oxidative environment into a char, and oxidised eventually into CO₂ beyond 500 °C.In inert conditions, the deacetylation step as well as the chain scission reaction shows endothermic effects. In an oxidative environment, large exothermal effects are found for each degradation step. This indicates the occurrence of additional oxidation reactions during deacetylation, an important reorganisation of the polyene during char formation and oxidation of the latter into CO₂.     

Influence of Fe‐MMT on the fire retarding behavior and mechanical property of (ethylene‐vinyl acetate copolymer/magnesium hydroxide) composite

In this work, Fe‐montmorillonite (Fe‐MMT) is synthesized and used as a synergistic agent in ethylene vinyl acetate/magnesium hydroxide (EVA/MH) flame retardant formulations. The synergistic effect of Fe‐MMT with magnesium hydroxide (MH) as the halogen‐free flame retardant for ethylene vinyl acetate (EVA) is studied by thermogravimetric analysis (TGA), limiting the oxygen index (LOI), UL‐94, and cone calorimetry test. Compared with that of Na‐MMT, it indicates that the synergistic effects of Fe‐MMT enhance the LOI value of EVA/MH polymer and improve the thermal stability and reduce the heat release rate (HRR). The structure and morphology of nanocomposites are studied by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The mechanical properties of the EVA composites have also been studied here, indicating that the use of Fe‐MMT reduces the amount of inorganic fillers. MH hence enhances the mechanical properties of the EVA composite while keeping the UL‐94 V‐0 rating. Copyright © 2008 John Wiley & Sons, Ltd.     

乙烯-醋酸乙烯酯-乙烯醇三元共聚物性质的研究

以乙烯-醋酸乙烯酯共聚物(EVA)为原料,通过控制VA的水解程度制得一系列不同组成的乙烯-醋酸乙烯酯-乙烯醇三元共聚物.研究表明:随水解程度的增加共聚物的结晶性越来越好.在一定水解度范围内共聚物具有良好的综合力学性能,是一种新型的热塑性弹性体.     

Chemical Modification of EVA for DrugRelease Application

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Effect of the liquid–liquid phase separation on the crystallization behavior of a poly(ethylene‐ran‐vinyl acetate) and paraffin wax blend

The effect of liquid–liquid phase separation (LLPS) on the crystallization behavior of poly(ethylene‐ran‐vinyl acetate) with a vinyl acetate content of 9.5 wt % (EVA‐H) in the critical composition of a 35/65 (wt/wt) EVA‐H/paraffin wax blend was investigated by small‐angle light and X‐ray scattering methods and rheometry. This blend exhibited an upper critical solution temperature (UCST) of 98°C, and an LLPS was observed between the UCST and the melting point of 88°C for the EVA‐H in the blend. As the duration time in the LLPS region increased before crystallization at 65°C, both the spherulite size and the crystallization rate of the EVA‐H increased, but the degree of the lamellar ordering in the spherulite and the degree of crystallinity of the EVA‐H in the blend decreased. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 707–715, 2000     

Synthesis of a Novel Flame Retardant and Its Synergistic Effect With a Phosphapheanthrene Flame Retardant in Polypropylene/Polyethylene Vinyl Acetate Blends

A novel flame retardant (NSiB) containing nitrogen, silicon and boron was synthesized through reacting of N-(β-aminoethyl)-γ-aminopropyl trimethoxy-silane (KH-792) and boric acid. The structure of NSiB was characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy with energy dispersive spectrometry (SEM-EDS). The effects of NSiB on the flame retardancy and thermal behaviors of polypropylene (PP)/polyethylene vinyl acetate (EVA) blends were investigated by limiting oxygen index value (LOI), vertical burning tests (UL-94) and thermal gravimetric analysis tests (TGA). The results showed that the flame retardancy and thermal stability of PP/EVA blends were improved with the addition of NSiB. When 7.5 wt% DOPO (phosphaphenanthrene) and 0.5 wt% NSiB were incorporated, the LOI value of the PP/EVA blends was 26.9%, and the class V-0 of UL-94 test was passed, as compared to the LOI value of 22.4% and class V-2 of UL-94 test for 8.0 wt% DOPO only and 16.7% and fail, respectively, for the PP/EVA blends alone. The char structure observed by SEM indicated that the surface of the char for the PP/EVA/7.5 wt% DOPO/0.5 wt% NSiB blends had a denser and continuous char structure when compared with that of the PP/EVA blends and PP/EVA/8.0 wt% DOPO blends. These results indicated that there was a good synergistic effect for NSiB and DOPO.     

Influence of char residues on flammability of EVA/EG, EVA/NG and EVA/GO composites

Graphite (expanded graphite(EG), natural graphite (NG) and graphite oxide (GO)) flame retardant poly(ethylene-co-vinyl acetate) copolymer (EVA) composites (EVA/EG, EVA/NG and EVA/GO) have been prepared by melt compounding. The flammability, the combustion process, the quantity of the residual char, the morphology of the residual chars and the thermal stability of the chars were investigated by cone calorimeter, SEM and TGA. The results indicate that heat release rate (HRR), total heat released (THR) and total smoke release (TSR) of EVA/EG (EG 30 phr) composite decrease to about 21%, 42% and 28% of that of pure EVA, respectively. The orders of the three kinds of graphite on the reduction effect of THR and TSR are EG > NG > GO. The higher the quantity, the higher is the thermal stability of the char residue and the more compact and porous char structure may be the main reasons for the phenomenon above. It has been found that the flame retardance of EVA vulcanisates is improved and the fire jeopardizing is dramatically reduced due to the addition of the graphite, especially for EG, which can give some advice to design formulations for practical applications as the jackets of cables.     

Kinetic Study of the Accelerating Effect of Coal-burning Additives on the Combustion of Graphite

The relationship between copolymer composition and transition temperatures was studied by means of differential scanning calorimetric analysis and dynamic mechanical spectroscopy. Six samples of ethylene vinyl acetate (EVA) copolymers containing from 5 to 40 mass per cent of vinyl acetate (VA) were studied. The differential scanning calorimetric analysis revealed that each EVA copolymer displays two endothermic peaks (T_m1 and T_m2 ) in the melting zone. Dynamic mechanical spectroscopy was used to determine the primary relaxation temperature (T_α ) for EVA copolymers. This latter characteristic is relatively insensitive to the level of vinyl acetate contained in the copolymer and is influenced by the pulsation frequency ω, also named the angular frequency. This revised version was published online in July 2006 with corrections to the Cover Date.     

使用本征值方法研究抗氧化剂的构效关系

利用本征值(EVA)方法对一组分子多样性较大的酚类或苯胺类抗氧化剂进行了理论研究,在未采用任何实验数据的情况下,研究结果接近于文献报道的QSAR模型,表明EVA方法是研究抗氧化剂抗氧化活性构效关系的良好工具.     

上市公司经营绩效评价方法的典型相关分析

本文介绍了上市公司经营绩效的传统评价方法和EVA、MVA方法,并对几种方法进行了比较,采用典型相关分析方法,以沪市180指标股的相关数据进行了实证研究。我们发现EVA类指标与传统财务评价指标的结论是相一致的,都是公司经营绩效的有效反映。