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1.
The efficiency of different techniques of obtain improved adhesion in polyethylene-aluminum laminates have been studied. Both surface treatments, such as thermal oxidation and corona discharge, and the use of copolymers with polar comonomers, i.e., vinyl acetate (EVA) and butyl acrylate (EBA), have been included. Thermal oxidation performed by high temperature extrusion including an ozone shower seems to be more effective than corona discharge. In a model experiment thermal oxidation was studied in more detail. The adhesion, as measured by a T-peel test, increased with the content of carbonyl measured by reflexion IR, except for relatively long thermal treatments. In the latter case molecular scission gave a large fraction of low molecular weight material with low cohesive strength. For EBA and EVA the peel strength increased linearly with the bulk concentration of comonomer from about 100 N/m for untreated polyethylene to 450 and 300 N/m, respectively, at 5 mol % comonomer. Corona discharge treatment of these copolymers had, however, a most remarkable effect on the adhesion properties. The increases, relative to untreated EBA and EVA, were much more dramatic compared to polyethylene, e.g., three to four and less than two times, respectively. The higher values obtained with EBA are suggested to be due to the conversion of acrylate groups into carboxylic acid. In the case of EVA, loss of acetic acid might instead decrease the content of polar groups.  相似文献   

2.
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.  相似文献   

3.
This is the first in a series of papers in which structural changes during thermal degradation of ethylene-vinyl acetate (EVA) and ethylene-butyl acrylate (EBA) copolymers are compared. EVA, containing 11.4 mol% vinyl acetate (VA) and EBA, containing 5.4 mol% butyl acrylate (BA), were pyrolyzed at 280°C in nitrogen for 30 min. In another series of pyrolysis, EVA containing 1.2, 2.2, and 11.4 mol% VA were treated at 150–190°C for 3 h. The volatile decomposition products were collected in cooled traps respectively gas bags and then analysed with GC-MS and ion-chromatography. EVA is rather labile. The main volatile decomposition product is acetic acid. A linear decomposition rate was found already at the lowest investigated pyrolysis temperature, 150°C. After 30 min at 280°C every 15th of the acetate side groups had been eliminated. EBA is much more stable to pyrolysis. Thirty minutes at 280°C resulted in a decomposition of one out of 1500 BA groups. Butene is the main volatile decomposition product. Ester pyrolysis is supposed to account for the degradation of both types of polymers. The big difference in reactivity is presumably due to conformational differences. The ester pyrolysis mechanism will result in random unsaturations in EVA and carboxylic groups in EBA. To a minor extent acetaldehyde is formed when EVA is degraded. According to the mechanisms suggested, carbonyl groups remain in the main chain. Contrary to what is reported for poly(butyl acrylate), no alcohol was formed when pyrolysing EBA. This indicates that adjacent acrylate groups are needed for alcohol formation. For both types of polymer, scissions of the main chain results in hydrocarbon fragments mainly. In addition, acrylate containing fragments are observed when EBA is degraded. EVA, however, does not give any acetate-containing fragments.  相似文献   

4.
Interfacial interactions to hydrated aluminium were examined for poly(ethylene-co-vinylacetate) EVA, poly(ethylene-co-butylacrylate) EBA, and poly(ethylene-co-acrylic acid) EAA. By means of IR reflection-absorption spectroscopy, the interactions between the effective functional groups were analysed at the polymer/aluminium interface. Thin copolymer films were prepared by solution casting onto aluminium, which had been hydrated by immersion in boiling water. The spectra representing the interface material revealed a strong hydrogen bond interaction between hydroxyl groups on the hydrated aluminium surface and the carbonyl oxygen in the ester group in EVA and EBA. The absorbance mode of the hydrogen bonded carbonyl was displaced to lower wavenumbers and appeared 34 cm-1 and 38 cm-1 below the 'free' carbonyl for EVA and EBA, respectively, which indicates that the hydrogen bond is very strong. For the C-O stretching mode in the ester group, a displacement of 36 cm 1 in the opposite direction was observed, also an effect due to the hydrogen bond to the carbonyl. Furthermore, it was found that the absorptivity for the hydrogen bonded carbonyl was much higher than for the 'free', and for that reason a relative absorptivity ratio between them was determined. For EAA cast onto hydrated aluminium surfaces, the absorbance mode of the carbonyl disappeared, but new peaks arose at lower wavenumbers indicative of a carboxylate. This was explained to be due to a reaction between carboxylic acid groups and aluminium hydroxyl groups on the hydrated surface.  相似文献   

5.
Mass spectra of a set of six vinyl monomers derived from stearic acid, each representative of one of the following groups: Vinyl ester (R? CO? O? CH?CH2), allyl ester (R? CO? O? CH2? CH?CH2), acrylic ester (RCH2O? CO? CH?CH2), methacrylic ester (RCH2O? CO? C[CH3]?CH2), allyl ether (RCH2OCH2CH?CH2), and vinyl ether (RCH2OCH?CH2), where R is CH3(CH2)16- are discussed with respect to the influence of the chemical environment on their fragment pattern.  相似文献   

6.
By immersing aluminum in boiling water, a hydroxyl-covered pseudoboehmite layer is formed on the aluminum surface. The adhesion strength between aluminum foils, hydrated in boiling water for short times, and ethylene copolymers, with vinyl acetate, n-butyl acrylate, and acrylic acid, was examined. The laminates were obtained by pressing with 1.2 MPa at 250°C and the peel strengths were measured by a T-peel test. By hydrating the aluminum foils, the adhesion strength was doubled for the ester copolymers, while a moderate effect was observed for the acrylic acid copolymer. To understand the adhesion mechanism, the chemical and topographic transformations were followed, using FTIR, SEM, TGA, and BET surface-area analysis. The adhesion mechanism was found to depend on many factors, such as mechanical effects and increased surface area, due to the porosity of the hydrated film formed. The improved adhesion after hydration of the aluminum can also be explained by the fact that new, stronger interactions are formed. A carboxylate formation of carboxylic acid groups and a catalyzed hydrolysis reaction of the ester bond at the interface is also proposed. These reactions change the functionality on the polymer surface and the formation of stronger bonds between the materials is possible. © 1993 John Wiley & Sons, Inc.  相似文献   

7.
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.  相似文献   

8.
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.  相似文献   

9.
The crosslinked structure of irradiated ethylene-vinyl acetate copolymer (EVA) film was examined by means of ESR, IR and pyrolysis-gas chromatography. The ESR spectrum of 35 Mrad irradiated EVA film with 95g kg?1 vinyl acetate content consisted of a three-line component with an intensity ratio of 1:2:1, a hyperfine structure coupling of 22.4 G and g factor of 2.0049. Therefore, the spectrum was assigned to the methylene radical with two α protons on the same plane; this radical is formed by loss of a hydrogen atom from the acetoxymethyl group. In pyrolysing EVA films at 500°C, the yield of acetic acid from 10 Mrad-150 g kg?1 film significantly decreased compared with that of unirradiated film, and it decreased with increasing crosslinking density. By measuring the IR spectra of methanolysed EVA films, the following results were obtained: the absorbances at 1740, 1250 and 1050cm?1, attributed to the C?O, O?C? O? R and C? O? C groups, respectively, had a marked decrease, whereas the three peaks for 20Mrad film were much stronger than those of unirradiated film. On the basis of these findings, it is suggested that the crosslinking reaction in electron beam irradiated EVA film with lower doses takes place between the acetoxy groups and the main chains.  相似文献   

10.
This is the second in a series of papers in which the thermal degradation of ethylene-vinyl acetate (EVA) and ethylene-butyl acrylate (EBA) copolymers are compared. The EBA samples contain 0.8, 1.6, and 5.4 mol % butyl acrylate (BA), respectively, and the EVA samples 1.2 and 6.7 mol % vinyl acetate (VA). The samples were heated in nitrogen in a tubular oven at 285, 333, 350, 370 and 390°C for 6–120 min. The samples were analyzed with IR, NMR, gravimetry, and titration of carboxylic groups. The EVA samples were rapidly degraded by deacetylation, which was complete after about 30 min at 333°C. A linear relation between the loss of acetate groups and the formation of trans double bonds was found. A small amount of keto groups and traces of lactones were also observed. The data confirm the previously proposed mechanisms for deacetylation and the formation of acetaldehyde. A mechanism for lactone formation is suggested. The deacetylation rate is increasing with the VA content, presumably because of an increased amount of block sequences and an enhanced acid catalytic effect. The acrylate sidegroups are much more stable than the acetate groups, and are similar in stability to the main hydrocarbon chain. The BA decomposition results in carboxylic and anhydride groups. Decarboxylation also occur and increases with the thermal treatment. In LDPE and EBA the increase in unsaturation is small and mainly due to vinyl end groups formed via β-cleavage or disproportionation. In EVA the formation of vinyl end groups is suppressed.  相似文献   

11.
本文研究了聚乙烯/乙烯-醋酸乙烯共聚物(PE/EVA)和聚乙烯/乙烯-丙烯酸共聚物(PE/EAA)的共混物以及马来酸酐(MAH)接枝聚乙烯(MAH-g-PE)与铝箔的粘结性能,红外光谱证实反应产物为接枝产物,并考查了热复合工艺条件(温度,压力,时间)对剥离强度的影响,同时,发现在MAH-g-PE中加入10%的EVA可明显提高铝箔的粘结性,扩大了非极性聚乙烯的应用范围。  相似文献   

12.
Four ethylene vinyl acetate copolymers (EVAs) containing 9, 12, 18 and 20 wt% vinyl acetate (VA) were treated with concentrated sulphuric acid to improve their adhesion to polychloroprene (PCP) adhesive. The tensile strength and Young's modulus of EVAs decreased as the VA content increased, due to the reduction in crystallinity of the polyethylene blocks in the copolymer. The modifications produced in the EVAs by treatment with sulphuric acid were followed using contact angle measurements (water, 25 °C), ATR-IR spectroscopy and scanning electron microscopy (SEM). Adhesive-bond strength was obtained by T-peel tests on treated EVA/polychloroprene adhesive joints. The vinyl acetate content in the EVA affected the extent, but not the nature, of the surface modification produced by treatment with sulphuric acid. The treatment produced both sulfonation and oxidation on the EVA surfaces. The higher the vinyl acetate content in the EVA, the more significant the modifications produced. Increased T-peel strengths of EVA/polychloroprene adhesive + 5 wt% polyisocyanate joints were obtained and a mixed failure (adhesion failure + cohesive failure in the adhesive) was produced. It was found that, to be effective, the treatment of EVAs must be carried out with 96 wt% sulphuric acid.  相似文献   

13.
EVA改性聚乙烯无卤阻燃泡沫塑料的研究   总被引:8,自引:0,他引:8  
张军  钱晓琳 《弹性体》2001,11(3):6-11
以乙烯-醋酸乙烯酯(EVA)改性低密度聚乙烯(LDPE),添加无卤阻燃剂氢氧化镁,采用高温混炼,化学交联,模压一步法来制备无卤阻燃改性PE泡沫,通过力学性能,扫描电镜,差示扫描量热法(DSC)3种测试方法,重点探讨了无卤阻燃剂Mg(OH)2对材料性能的影响以及EVA改性剂,协同阻燃剂三氧化二锑(Sb2O3),交联剂过氧化二异丙苯(DCP),发泡剂偶氨二甲基酰胺(AC),发泡剂N,N′-二亚硝基戊次甲基四胺(H),填料等因素对无卤阻燃改性PE泡沫塑料性能的影响。实验结果表明:选择LDPE70份,醋酸乙烯(VA)质量分数33%的EVA30份,Mg(OH)2140份,AC4份,H4份,DCP0.8份,三盐基硫酸铅(3PbO)1份,二盐基亚磷酸铅(2PbO)1份,复合盐1份,硬脂酸(SA)1份,硬脂酸钡(BaSt)2份可制得阻燃性能,力学性能和加工性能较好的改性PE泡沫塑料。  相似文献   

14.
This is the third in a series of papers in which the thermal degradation of ethylene-vinyl acetate (EVA) and ethylene-butyl acrylate (EBA) copolymers are compared. The EBA samples contained 0.8, 1.6, and 5.4 mol % butyl acrylate (BA), respectively, and the EVA samples 1.2 and 6.7 mol % vinyl acetate (VA). The samples were heated in nitrogen in a tubular oven at 285–390°C, for 6–120 min. The molecular weight distribution (MWD), long chain branching, and gel content were analyzed with size exclusion chromatography (SEC). The columns were connected to refractive index, viscometric, and light scattering detectors. EVA gave a pronounced molecular enlargement at all degradation temperatures. In EVA-6.7, gel was formed at all degradation levels, whereas the low content sample, EVA-1.2, did not form any visible amount of gel. The strong tendency to molecular enlargement is due to allyl radicals formed after thermal deacetylation and the formation of internal double bonds. These macroradicals will combine or, less frequently, add to double bonds. The EBA copolymers show a more polyethylenelike degradation behavior. At 285°C molecular enlargement dominates, but already at 333°C a net reduction in molecular size is observed. At high temperatures, ester pyrolysis of the BA groups give carboxylic groups and anhydrides. Alkaline treatment will not give any appreciable change in MWD, showing that the anhydride formation is mainly intramolecular. The chain scission increases with the BA content. This is probably due to β-cleavage of tertiary macroradicals formed in the chain at the acrylate or carboxylic side groups.  相似文献   

15.
The corona discharge technique was explored as a means of forming chemically active sites on a low‐density polyethylene (LDPE) film surface. The active species thus prepared at atmospheric pressure in air was exploited to subsequently induce copolymerization of 2‐hydroxyethyl methacrylate (HEMA) onto LDPE film in aqueous solution. The results showed that with the corona discharge voltage, reaction temperature, and inhibitor concentration in the reaction solution the grafting degree increased to a maximum and then decreased. As the corona discharge time, reaction time, and HEMA concentration in the reaction solution increased, the grafting degree increased. With reaction conditions of a 5 vol % HEMA concentration, 50°C copolymerization temperature, and a 2.0‐h reaction time, the degree of grafting of the LDPE film reached a high value of 158.0 μg/cm2 after treatment for 72 s with a 15‐kV voltage at 50 Hz. Some characteristic peaks of the grafted LDPE came into view at 1719 cm?1 on attenuated total reflectance IR spectra (C?O in ester groups) and at 531 eV on electron spectroscopy for chemical analysis (ESCA) spectra (O1s). The C1s core level ESCA spectrum of HEMA‐grafted LDPE showed two strong peaks at ~286.6 eV (? C ? O? from hydroxyl groups and ester groups) and ~289.1 eV (O?C ? O? from ester groups), and the C atom ratio in the ? C? O? groups and O?C? O groups was 2:1. The hydrophilicity of the grafted LDPE film was remarkably improved compared to that of the ungrafted LDPE film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2881–2887, 2001  相似文献   

16.
The transesterification reaction in the molten state of ester groups of ethylene vinyl acetate (EVA) copolymers and ethylene acrylic ester (EMA) copolymers has been used to crosslink the chains of this polymeric system. The relative EVA copolymers (or EMA copolymers) concentration dependence of the network formation by co-crosslinking of EVA/EMA miscible blends has been assessed. EVA/EMA networks were characterized by swelling experiments, rheological measurements, and determination of the extent of the reaction through a chromatographic technique. All results can be compared in a master curve. The influence of the polydispersity and the microstructure of EVA and EMA samples was put in evidence. On the other hand, a scaling law (v2~Mc?3/5) was observed in agreement with predictions of the Flory-Rhener expression. © 1994 John Wiley & Sons, Inc.  相似文献   

17.
通过采用铝酸酯偶联剂和硬脂酸对淀粉表面进行改性处理,并添加相容剂的方法制备了高含量淀粉/HDPE复合片材,比较了乙烯-醋酸乙烯酯共聚物(EVA)和马来酸酐接枝PE(PE-g-MAH)两种相容剂对片材的增强作用。结果表明,通过增容改性处理,高含量淀粉/HDPE片材的拉伸强度有了显著的提高,采用1%铝酸酯和2%的硬脂酸对淀粉进行改性并添加5%的PE-g-MAH时,片材的拉伸强度保持在25 MPa以上。通过显微镜镜像观察,改性处理后淀粉与HDPE之间的相容性有了明显改善。  相似文献   

18.
Ethylene vinyl acetate (EVA) copolymer with varying vinyl acetate (VAc) content, viz. 18%, 28% and 40% has been hydrolyzed using alcoholic NaOH solution. Fourier Transform Infrared Spectroscopy (FTIR) analyses of hydrolyzed polymer showed the presence of both OH group and acetate group indicating that the EVA has been partially hydrolyzed. Differential Scanning Calorimeter (DSC) and Thermo Gravimetric Analyzer (TGA) of EVA and hydrolyzed EVA showed large difference in melting and decomposition temperature, respectively. Hydrolyzed EVA showed higher tensile strength and elongation at break compared to corresponding EVA. Blends of different grades of EVA and ethylene vinyl alcohol (EVAl) with low density polyethylene (LDPE) were applied on grit blasted mild steel surface by flame spray technique. FTIR analysis of blends before and after coating showed no degradation during flame spray. Measurement of adhesion strength of these coating showed that adhesion strength increased on hydrolysis of EVA.  相似文献   

19.
Glow discharge polymerizations of tetramethylsilane (TMS) were performed by the capacitive coupling of a 20 kHz frequency in comparison with those by the inductive coupling of a 13.56 MHz frequency. The polymers prepared by the former coupling were poorer in carbon and hydrogen, but richer in silicon than those prepared by the latter coupling. These two polymers showing similar infrared spectra contained CH3, CH2, CH, Si? O? C, Si? O? Si, Si? CH3, and Si? CH2? CH2? Si groups. Some physical properties involving surface energy, thermal stability, and absorption spectra in the regions of the UV and visible light were determined. This coating procedure was applied for surface hardening of a polyethylene sheet. The surface hardness of the polyethylene sheet was enhanced by a coating of plasma films prepared from TMS or the TMS/O2 mixtures. Surface hardness was determined by the pencil method and hardness was enhanced from 2B to 2H. The adhesion between these plasma films and polyethylene sheet was good even when immersed in 0.9% NaCl solution at 40°C for 10 days.  相似文献   

20.
The radiation‐induced crosslinking, compatibility, and surface modification of low density polyethylene/ethylene vinyl acetate blends (LDPE/EVA) were investigated. The structural and physical properties were characterized in terms of gel content, hot set, mechanical properties, contact angle, and surface free energy. The highest crosslink density was obtained at 20 wt % of EVA. Gel content of LDPE/EVA blends was increased with increasing irradiation dose, vinyl acetate (VA), and EVA contents. The hot set results are consistent with the gel content data. Mechanical testing showed that the tensile strength of samples increased with increasing irradiation dose up to 180 kGy, whereas the elongation at break was decreased with increasing irradiation dose. Contact angle measurements showed that the surface hydrophillicity of LDPE blend was increased with increasing irradiation dose and contents of both VA and EVA. The surface free energy was greatly dependent on irradiation dose and content of both VA and EVA. The total surface free energies of different LDPE formulations were in the range 17.25–32.51 mN/m, in which the polar (pσ) and disperse (dσs) values were within the range 16.52–26.6 and 0.9–5.91 mN/m, respectively. In conclusion, electron beam irradiation and blending LDPE with EVA improved the wettability or adhesion properties of LDPE/EVA blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

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