EVA生产情况和市场前景分析

<正>EVA树脂是由乙烯和醋酸乙烯在一定的温度和高压下进行本体聚合而成,是由不同链长及链结构的聚合物分子组成的一种聚合物,占LDPE(低密度聚乙烯)共聚物的75%左右。EVA树脂中醋酸乙烯(以下简称VA)的含量一般在5%~40%(质量分数,下同),平均分子量在10000~30000。与LDPE相比,EVA树脂由于在分子链中引入了VA单体,提高了聚合物的支化度,从而降低了结晶度,提高了柔     

EVA树脂性能及用途

EVA树脂不仅是生产胶粘剂的主要原料之一,而且还可以广泛地应用到其他领域。本文从应用的角度,系统地介绍了EVA树脂的性能——MFR、VA％与分子量、熔融粘度、硬度、弹性系数、抗拉强度、伸长度、环球软化温度、结晶度、玻璃化温度和熔点的关系,以及EVA树脂的主要优点和用途。     

聚苯硫醚的差示扫描量热分析

通过 DSC法测定不同聚苯硫醚 (PPS)树脂的热性能。结果表明 ,不同 PPS树脂的玻璃化转变温度、最快结晶速率温度和熔融温度相近时 ,树脂的加工和纺制的纤维的性能与结晶性能有明显关系。PPS相对分子质量对结晶性能的影响很敏感。采用新的数据处理方法获得了整个可结晶温度区间的结晶动力学参数。     

不同反应压力下乙烯-乙酸乙烯酯树脂的制备及研究

在不同反应乙烯压力下制备乙烯-乙酸乙烯酯(EVA)共聚物,研究不同反应乙烯压力对EVA分子结构、树脂固含量、玻璃化转变温度(Tg)和特性粘数[η]的影响,并用热裂解法对EVA和乙烯-乙烯醇共聚物(EVOH)进行分析。研究表明,随着反应压力的升高,EVA分子结构中的亚甲基质子峰开始向高磁场移动,树脂固含量逐渐增加,玻璃化转变温度(Tg)和特性粘数[η]逐渐降低,并且1.533 min处的峰是EVA分子中乙酸酯基团的热裂解特征峰。     

不同VA含量EVA／硅橡胶共混物的性能

研究了VA含量(0～28％)对EVA/硅橡胶共混物力学性能和结晶性能的影响。试验结果表明:VA含量为17—21％范围内的EVA/硅橡胶共混物具有最大的拉仲强度;用EVA/LDPE共混材料代替相同VA含量的EVA与硅橡胶共混,得到的共混物具有相似的力学性能;VA含量增加,EVA的结晶度降低,熔点降低。     

硅橡胶的低温性能

综述了硅橡胶的低温性能,包括玻璃化转变过程,结晶过程和低温力学性能。改善硅橡胶低温性能的主要手段是通过共聚改性在聚二甲基硅氧烷分子链上引入其它大体积基团。适合的改性链节既可调节硅橡胶的玻璃化温度,也可有效抑制结晶过程,提高硅橡胶的低温弹性。     

高压釜式法EVA生产及产品性能分析北大核心

分析了反应温度、压力和引发剂种类对乙烯-乙酸乙烯酯共聚物(EVA)生产的影响,确定了EVA开车条件,生产了可用于注塑、预涂膜、热熔胶等的EVA产品,并从分子链结构、聚集态结构、基础性能等方面对不同产品的性能进行分析和比较。结果表明:乙酸乙烯酯(VA)含量接近的情况下,EVA的熔体流动速率(MFR)增加,剪切黏度降低;MFR相似的情况下,VA含量增加,EVA的剪切黏度增加。高压釜式法EVA的重均分子量、数均分子量较高,具有更好的加工性能,确立了釜式法生产EVA的优势和方向。     

邻苯二甲酸二辛酯对PLA／EVA共混物性能的影响

研究了增塑剂邻苯二甲酸二辛酯（DOP）对聚乳酸／乙烯-醋酸乙烯酯弹性体（PLA／EVA）共混物力学、热学和结晶性能的影响。结果表明：PLA／DOP（100／20）共混物的缺口冲击强度、无缺口冲击强度及断裂伸长率比纯PLA分别提高了183％、197％和667％，共混物中PLA的玻璃化转变温度和熔融温度分别降低21．0℃和18．3℃，结晶度提高42％；PLA／EVA／DOP（80／20／8）的缺口冲击强度、无缺口冲击强度及断裂伸长率比PLA／EVA（80／20）分别提高了47％、57％和148％，共混物中PLA的玻璃化转变温度和熔融温度分别降低90℃和11.5℃，结晶度提高11％；DOP的加入会使EVA粒子在PLA中的分散度和均一性更佳。     

PET化学结构与热力学行为的关系

采用差热分析和红外光谱分析、粘均相对分子质量测定的方法,研究了PET的相对分子质量、端羟基和端羧基含量等化学结构与其玻璃化转变、冷结晶、热结晶行为、熔融行为的关系。结果表明:由于玻璃态中分子链段的局部有序性,PET呈现出双玻璃化转变和双冷结晶峰;随着相对分子质量减小,端羟基和端羧基含量相对增加,PET的玻璃化转变温度升高,冷结晶能力和热结晶能力增强,熔点升高,有利于形成结构完善的增强微纤。相对分子质量和端羧基、端羟基含量对热结晶行为影响的程度比对冷结晶行为的大得多,热结晶过程也由均相成核到既有异相成核,又有均相成核,到以异相成核为主。     

氯化钙对尼龙612聚集态结构的影响

采用差示扫描量热仪（DSC）、广角X射线衍射仪（WAXD）、傅立叶红外光谱仪（FTIR）方法研究了氯化钙对尼龙612聚集态结构的影响。结果表明，氯化钙的引入，破坏了尼龙612的结晶，使其由结晶态转变成无定形。红外光谱结果证实钙离子能够插入尼龙612分子链，破坏尼龙612的氢键，与尼龙612分子链上的羰基发生配位作用，使尼龙612由结晶态转变为无定形态。     

动态交联PP/EVA共混物的制备与性能研究

本文将动态交联技术应用于PP/EVA共混体系中,制得动态交联PP/EVA共混物。采用Hakke转矩流变仪研究了动态交联对PP/EVA共混物扭矩的影响;研究了DCP和EVA含量对共混物力学性能的影响;考察了动态交联共混物的维卡软化点。结果表明：加入DCP后,PP/EVA共混物扭矩先升后降,DCP的添加量为EVA含量的1%为宜。随EVA用量的增加,动态交联EVA/PP共混物的冲击强度大幅提高,但拉伸强度有所降低。少量经动态交联的EVA颗粒可以促进共混物中PP的结晶, 提高共混物的维卡软化点。     

Adhesion and rheological properties of EVA-based hot-melt adhesives

Ethylene vinyl acetate (EVA) copolymers of various melt indexes were blended with aromatic hydrocarbon resin in the molten state, and the thermal and adhesion properties as hot-melt adhesives (HMAs) were investigated. The thermal properties for the EVA blends with aromatic hydrocarbon resin were studied using differential scanning calorimeter, Brookfield viscometer and dynamic mechanical thermal analyzer. Their adhesion strength was also obtained using single lap shear strength. The examination of thermal properties for the blend of EVA copolymers with aromatic hydrocarbon resin over a large temperature range showed that the glass transition temperature was independent of their melt index (MI), but that their heat of fusion decreased with increasing MI of EVA copolymers. Furthermore, the storage and loss moduli of the blends decreased with increasing temperature and MI of EVA copolymers, but the loss tangent (tan δ) of the blends increased. An increase in the MI of EVA copolymers decreased the adhesion strength of the blend at the same test condition.     

Peel adhesion and viscoelasticity of poly(ethylene-co-vinyl acetate)-based hot melt adhesives. I. The effect of tackifier compatibility

A series of poly(ethylene-co-vinyl acetate) (EVA)-based hot melt adhesives containing either a rosin or a hydrocarbon (C5–C9) tackifier have been prepared to investigate viscoelastic properties and peel adhesion. Fracture energies were determined by the use of a T-Peel geometry (two polypropylene films bonded with model EVA adhesives). The rosin has only one glass transition temperature, but the C5–C9 resin has two glass transition temperatures, indicating phase separation. The rosin has better compatibility with EVA than does the C5–C9 resin. The bond strength of tackified EVA to polypropylene depends not only on compatibility, but also on viscoelastic properties. A higher storage modulus results in a higher T-Peel strength. Under certain test conditions, glassy C5–C9-rich domains act as reinforcing filler, resulting in a higher storage modulus. Here, a C5–C9-tackified EVA adhesive has higher T-Peel strength than does one containing rosin. © 1997 John Wiley & Sons, Inc.     

Effect of styrene–ethylene–butadiene–styrene and its synergetic effect with ethylene vinyl acetate on the mechanical,thermal, dielectric,and water‐treeing behaviors of crosslinked polyethylene

In this study, we investigated the effect of an aromatic polymer, styrene–ethylene–butadiene–styrene (SEBS), on the water‐tree resistance of crosslinked polyethylene (XLPE), and the synergetic effect of SEBS and ethylene vinyl acetate (EVA) was also investigated. The XLPE/SEBS and XLPE/SEBS/EVA samples were characterized by means of differential scanning calorimetry, scanning electron microscopy, mechanical measurements, and an accelerated water‐treeing experiment, and the obtained results clearly show the relevant influence of SEBS and EVA, and as expected, the addition of SEBS and EVA was found to synergistically influence the water‐tree resistance of XLPE more positively in comparison with that without the addition of EVA. In addition, it also indicated that the blends possessed excellent dielectric behaviors, such as the dielectric constant and dissipation factor. The crystallization of the blends decreased with increasing SEBS content and addition of EVA. However, the melting temperature of the blends increased with the addition of SEBS and EVA, but the melting temperature of the blends decreased with increasing SEBS content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of processing condition and HA content on the crystallization behavior of HA‐filled EVA biocomposite

Hydroxyapatite/ethylene‐vinyl acetate (HA/EVA) composites with a HA content of 30 and 50 wt% were prepared by injection molding. The crystallization behaviors of EVA under different injection pressure, annealing temperature, and HA content were investigated. Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and scanning electron microscope were used to evaluate the composites. The result of FTIR analysis infers the occurrence of hydrogen bonding between HA and EVA. XRD and DSC analyses show that the increasing injection pressure can accelerate the crystallization rate of EVA but it tends to decrease the crystallization degree slightly, which may be caused by the increase of EVA segmental activity and the loss of EVA crystallization order with the increase of pressure. The EVA crystallization degree can be improved by the annealing process. It is found that HA can induce more nucleation sites of EVA, but the crystallization degree of EVA decreases with the increase of HA content. The large content of HA acts to reduce the mobility of EVA crystallizable chain segments and inhibits the crystal growth of EVA. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Mechanical properties of ethylene–vinyl acetate/polystyrene blends studied by in situ polymerization

This study examined ethylene–vinyl acetate (EVA)‐toughened polystyrene (PS). EVA is well‐known to be incompatible with PS; thus, the PS graft to the EVA backbone (EVA‐g‐PS) was used as a compatibilizer and provided good adhesion at the interface of PS and EVA. In addition, the mechanical properties and impact resistance of the PS matrix were obviously improved by EVA‐g‐PS and by EVA itself. Meanwhile, differential scanning calorimetry results showed that the grafted PS chain influenced the crystallization of EVA; for example, the melting temperature, the crystallization temperature, and the percentage crystallinity related to EVA were reduced. Moreover, the addition of 10% EVA increased the impact strength by a factor of five but reduced the modulus by the same factor. Additionally, a lower number‐average molecular weight EVA delayed phase inversion and resulted in poor mechanical properties. A fracture surface photograph revealed that the major mechanism of EVA‐toughened PS was craze and local matrix deformation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 699–705, 2003     

Viscoelastic and adhesion properties of hot-melts made with blends of ethylene-co-n-butyl acrylate (EBA) and ethylene-co-vinyl acetate (EVA) copolymers

Several hot-melts (HMAs) were prepared by using blends of ethylene-co-n-butyl acrylate (EBA) and ethylene-co-vinyl acetate (EVA) copolymers - EBA/EVA. HMAs were prepared with mixtures of EVA copolymers with 18 (EVA18) and 27 (EVA27) wt% vinyl acetate contents and EBA copolymer with 27 wt% n-butyl acrylate, polyterpene resin and mixture of microcrystalline and Fischer-Tropsch waxes. HMAs made with EBA/EVA blends showed lower viscosities and reduced shear thinning than the ones made with EBA or EVA due to differences in compatibility, but both the set time and the open time were not affected as they depended mainly on the wax nature and amount. The increase of the vinyl acetate (VA) content in EVA copolymer reduced the crystallinity of the EBA/EVA blends. Even EBA copolymer was more compatible with EVA27 than with EVA18 (the α- and β-transitions shown in DMTA plots were closer) and the compatibility did not vary with the EBA content in the blends. The addition of polyterpene resin and the mixture of waxes decreased the compatibility of the EBA/EVA blends, the higher compatibility was observed for the HMAs made with only one copolymer. The tack of the HMAs depended on their EBA/EVA contents, EBA/EVA27 HMAs showed broader temperature interval with higher tack, while the tack of EBA/EVA18 HMAs blend decreased and the temperature interval with tack was shortened and shifted to lower temperatures. Adhesion to polypropylene film was improved in HMAs made with 75 wt% EBA/25 wt% EVA18 and 50–75 wt% EBA/50-25 wt% EVA27. The adhesion to aluminum film of EBA or EVA hot melts was improved only in the joints made with EBA/EVA 27 HMAs, more noticeably when they contained higher EBA content.     

Viscoelastic,thermal, and morphological analysis of HDPE/EVA/CaCO<Subscript>3</Subscript> ternary blends

High density polyethylene (HDPE), calcium carbonate (CaCO₃), and ethylene vinyl acetate (EVA) ternary reinforced blends were prepared by melt blend technique using a twin screw extruder. The thermal properties of these prepared ternary blends were investigated by differential scanning calorimetry. The effect of EVA loading on the melting temperature (T _m) and the crystallization temperature (T _C) was evaluated. It was found that the expected heterogeneous nucleating effect of CaCO₃ was hindered due to the presence of EVA. The melt viscosities of the ternary reinforced blends were affected by the % loading of CaCO₃, EVA, and vinyl acetate content. Viscoelastic analysis showed that there is a reduction of the storage modulus (G′) with increasing of EVA loading as compared to neat HDPE resin or to HDPE/CACO₃ blends only. The morphology of the composites was characterized by scanning electron microscopy (SEM). The dispersion and interfacial interaction between CaCO₃ with EVA and HDPE matrix were also investigated by SEM. We observed two main types of phase structures; encapsulation of the CaCO₃ by EVA and separate dispersion of the phases. Other properties of ternary HDPE/CaCO₃/EVA reinforced blends were investigated as well using thermal, rheological, and viscoelastic techniques.     

Crystal orientations and structures of poly(ethylene-ran-vinyl acetate) films coated onto silicon substrates

The crystal orientations and structures of poly(ethylene-ran-vinyl acetate) (EVA) films coated onto silicon substrates to a thickness of 5–200 nm were investigated by performing isothermal crystallization of the films. Bulk-like isotropic crystal orientations and orthorhombic crystalline phases were observed in films thicker than 50 nm. In the thinner films (<50 nm), the crystal orientations remained edge-on (with the chain axis parallel to the substrate), and two crystal structures, orthorhombic and hexagonal, were observed. The preference for an edge-on orientation was attributed to surface nucleation and repulsive interactions between the crystallizable ethylene components and the substrate. An orthorhombic structure developed at the surface from the primary crystallization during isothermal crystallization. A hexagonal structure formed near the interface as a result of secondary crystallization after cooling to room temperature. These results are discussed in terms of the favorable interactions between the polar vinyl acetate and the substrate, which affect the crystallization of the ethylene component in thin EVA films.     

CHARACTERIZATION OF EVA-BASED ADHESIVES CONTAINING DIFFERENT AMOUNTS OF ROSIN ESTER OR POLYTERPENE TACKIFIER

Different amounts (50-170 php--parts per hundred parts of EVA, 33-63 wt%) of two tackifiers (hydrogenated rosin ester, polyterpene resin) were added to an ethylene vinyl acetate (EVA) copolymer containing 28 wt% vinyl acetate. The EVA and the tackifier were characterized using infrared (IR) spectroscopy, DSC measurements, and stress-controlled plate-plate rheology. The properties and compatibility of the EVA-tackifier mixtures were studied using DSC, DMTA, and stress-controlled plate-plate rheology. Immediate adhesion was measured as a quantification of tack, and the T-peel strength of roughened styrene-butadiene rubber/EVA-tackifier adhesive joints was also obtained. The increase in the amount of tackifier noticeably changed the crystallinity of polyethylene blocks in the EVA, and the temperature at the cross-over between the curves of the storage and loss moduli as a function of the temperature was displaced to a lower value. Whereas the hydrogenated rosin ester was compatible with the amorphous ethylene vinyl acetate copolymer regions of the EVA (Tg value increased) reducing its crystallinity, the polyterpene resin was compatible with the polyethylene blocks of the EVA (T g value was not modified), increasing its crystallinity. Immediate adhesion of the EVA-tackifier mixtures was improved by adding both hydrogenated rosin ester and polyterpene tackifiers. On the other hand, there was an optimum tackifier content at which the maximum T-peel strength value was obtained.