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.     

Influence of the vinyl acetate content and the tackifier nature on the rheological,thermal, and adhesion properties of EVA adhesives

Three ethylene vinyl acetate (EVA) copolymers with different vinyl acetate (VA) contents (28-40 wt%) were mixed with rosin ester and polyterpene resin tackifiers in a 1 : 1 (weight/weight) ratio. The rheological and thermal properties of the tackifiers were determined and the use of rheological measurements as a precise way to measure the softening point of the tackifiers is proposed. The glass transition temperature of the tackifiers was obtained from the second heating run, after the thermal history of the tackifiers was removed. The addition of the rosin ester to EVA produced a compatible mixture, whereas for the terpene resin a less compatible mixture was obtained. The increase in the VAamount decreased the crystallinity of EVAand both the storage and the loss moduli also decreased, but the peel strength and the immediate adhesion were increased. The immediate adhesion of EVA/tackifier blends was affected by both the compatibility and the rheological properties of the blends. In fact, a relationship between the mechanical storage modulus (E^t′) - obtained from DMTA experiments - of the adhesives and the immediate adhesion to thin rubber substrates was obtained. The adhesives containing the T tackifier showed higher moduli than those containing the G tackifier, and therefore higher peel strength values were obtained. An increase in the VA content increased the flexibility of the adhesives and thus a decrease in peel strength was obtained.     

Miscibility Between Ethylene Vinyl Acetate Copolymers and Tackifier Resins

A series of ethylene vinyl acetate copolymer (EVA) were blended with various kinds of tackifiers and the miscibility between the components was investigated. The miscibility of the blend is illustrated as a phase diagram. The EVA and modified rosin systems tended to have a phase diagram with lower critical solution temperature (LCST), whereas the EVA and petroleum resin systems tended to have that with upper critical solution temperature (UCST). The phase diagrams of EVA/tackifier resins systematically changed as VAc content in the copolymer increased, which is accounted for by the classical Flory-Huggins theory.     

Miscibility Between Ethylene Vinyl Acetate Copolymers and Tackifier Resins

A series of ethylene vinyl acetate copolymer (EVA) were blended with various kinds of tackifiers and the miscibility between the components was investigated. The miscibility of the blend is illustrated as a phase diagram. The EVA and modified rosin systems tended to have a phase diagram with lower critical solution temperature (LCST), whereas the EVA and petroleum resin systems tended to have that with upper critical solution temperature (UCST). The phase diagrams of EVA/tackifier resins systematically changed as VAc content in the copolymer increased, which is accounted for by the classical Flory-Huggins theory.     

Effects of hydrocarbon tackifiers on the adhesive properties of contact adhesives based on polychloroprene - III. The effect of the molecular weight of the tackifier

Aromatic hydrocarbon resins with different molecular weights (M_w = 1300-50400 daltons) were added to a solvent-based polychloroprene adhesive. The hydrocarbon resins were characterized using infra-red (IR) and differential scanning calorimetry (DSC) measurements. The properties and compatibility of the polychloroprene/resin blends were studied using mechanical tests, DSC measurements, scanning electron microscopy (SEM), and stress-controlled rheology. Tack measurements were also carried out and the adhesion strength was obtained from T-peel tests on roughened styrene-butadiene rubber/polychloroprene adhesive joints. The addition of low-molecular-weight tackifiers produced a compatible polychloroprene/tackifier system (only one T_g was found in DSC measurements), while the addition of a high-molecular-weight (and broad molecular weight distribution) tackifier produced a partially incompatible system (two Tg's were found in DSC measurements). The compatibility of polychloroprene/tackifier blends was also assessed with stress-controlled rheology and SEM. An increase in the T-peel strength and tack were produced when the molecular weight of the tackifier increased, although the addition of a hydrocarbon resin with a M_w higher than about 50 000 reduced the tack. A broad molecular weight distribution in the tackifier favoured incompatibility with the polychloroprene, resulting in a reduction in the tack and rheological properties.     

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.     

Improved adhesion of EVAs with different vinyl acetate contents treated with sulphuric acid

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.     

过氧化物交联改性PE-HD/EVA防水材料的研究

用过氧化二异丙苯（DCP）交联法改善高密度聚乙烯/乙烯醋酸乙烯共聚物（PE-HD/EVA）防水材料的尺寸稳定性,研究了交联剂用量对PE-HD/EVA片材热稳定性和力学性能的影响。采用傅里叶变换红外光谱仪、差示扫描量热仪、X射线衍射仪、索氏提取交联度测试法等对片材进行了分析,研究了片材力学性能的影响因素。结果表明,随着交联度的增大,片材的软化温度和结晶度逐渐降低,晶体结构基本不变,晶粒尺寸减小, 拉伸强度提高;当DCP用量为1.2 %（质量分数,下同）时,片材的拉伸强度达到了最大值,其断裂伸长率比未交联片材降低了77 %,尺寸稳定性得到明显改善;交联改性对于PE-HD/EVA解决防水材料尺寸稳定性差等问题具有一定的指导意义。     

Temperature dependence of tack and pulse NMR analysis of polystyrene block copolymer/tackifier system

The influence of tackifier structure on the temperature dependence of tack for a polystyrene block copolymer/tackifier system was investigated. A blend of polystyrene-block-polyisoprene-block- polystyrene triblock and polystyrene-block-polyisoprene diblock copolymers was used as the base polymer. Four different tackifiers were used: special rosin ester resin (RE), rosin phenolic resin (RP), hydrogenated cyclo-aliphatic resin (HC), and aliphatic petroleum resin (C5). Tack at 20?°C increased with the tackifier content for both RE and HC tackifier systems. Tack is affected by two factors: the work of adhesion at the adherend interface and the viscoelastic properties of the adhesive. The good balance of these two factors brought high tack. The adhesive with 10 wt.% tackifier exhibited the highest tack at 20?°C, whereas those with 30 and 50 wt.% tackifier were lower than those systems with 10 wt.% of the RP or C5 tackifiers. The adhesive with overly high hardness lowered the work of adhesion and the tack was not improved with more than 30 wt.%. A compatibility test in toluene solution and in solid state showed that tackifier RE has good compatibility with both polyisoprene and polystyrene, whereas tackifier RP has lower compatibility. Tackifiers HC and C5 had good compatibility with polyisoprene, but poor compatibility with polystyrene, and that of C5 was poorer. Pulse nuclear magnetic resonance (NMR) analyses indicated that tackifiers RE and HC effectively restrict the molecular mobility of polyisoprene phase.     

用酯化改性的歧化松香作增粘剂制备EVA热熔胶的初步研究

研究了以歧化松香为原料,用甘油和季戊四醇进行酯化改性,并以改性产物作为增粘剂制备EVA热熔胶。初步讨论了多元醇的用量、反应温度及催化剂对酯化反应的影响。实验结果表明,歧化松香与多元醇物质的量比为1:1左右,反应温度为260～270℃,催化剂次磷酸的加入量为总反应物的0．16%,且分批加入时,合成的歧化松香酯的性能较为优良。以合成的歧化松香甘油酯和歧化松香季戊四醇酯作为增粘剂制备的EVA热熔胶,固化时间均为5s,T型剥离强度可分别达到5．1 kN/m和2．8 kN/m。     

Synthesis and characterization of new thermoplastic polyurethane adhesives containing rosin resin as an internal tackifier

Three thermoplastic polyurethane elastomers (TPUs) were prepared using the prepolymer method. MDI (diphenylmethane-4,4′-diisocyanate) and the polyadipate of 1,4-butanediol (M_w = 2400) were reacted to produce a prepolymer containing unreacted isocyanate groups; chain extenders were different mixtures of 1,4-butanediol and a rosin resin (0-50%). The specific feature of this procedure was the introduction of a rosin resin as an internal tackifier to provide higher immediate adhesion to the TPUs. The new TPUs were characterized using gel permeation chromatography, wideangle X-ray diffraction, differential scanning calorimetry, stress-controlled rheology, and stress-strain measurements. The TPUs were used as raw materials to prepare solvent-based polyurethane adhesives, the adhesion properties of which were obtained from T-peel tests on PVC/polyurethane adhesive/PVC and leather/polyurethane adhesive/PVC joints. The addition of rosin resin as an internal tackifier contributed to the production of two types of hard segments, which affected the properties of the TPUs. Therefore, rosin resin as an internal tackifier produced an increase in the average molecular weight, an increase in the viscosity, and improved the rheological properties. The glass transtition temperature decreased if the TPUs contained rosin resin, due to a greater degree of incompatibility between the hard and soft segments. Consequently, slower kinetics of crystallization was obtained in the TPUs containing rosin resin. Depending on the amount of rosin resin in the TPU, different structures and properties were obtained. On the other hand, the immediate T-peel strength in all joints was improved if the TPU contained rosin resin.     

Characterization of thermoplastic polyurethane adhesives with different hard/soft segment ratios containing rosin as an internal tackifier

Three thermoplastic polyurethanes (TPUs) containing different hard/soft (h/s) segment ratios (1.05-1.4) were prepared using the prepolymer method. MDI (diphenylmethane-4,4′diisocyanate) and polyadipate of 1,4-butanediol (M _w = 2440) were allowed to react to produce the prepolymer. To provide the polyurethanes with high immediate adhesion to different substrates, a rosin + 1,4-butanediol mixture (1 : 1 equivalent%) was used as chain extender (TPU-Rs). These TPU-Rs had two types of hard segments: (i) Urethane hard segments, produced by reaction of the isocyanate and the 1,4-butanediol, and (ii) Urethan-amide hard segments, produced by reaction of the isocyanate and the carboxylic acid functionality of the rosin. The TPUs and TPU-Rs were characterized using FTIR spectroscopy, gel permeation chromatography, differential scanning calorimetry, stress-controlled plate-plate rheology, stress-strain measurements, and Brookfield viscosity. The TPUs and TPU-Rs were used as raw materials to prepare solvent-based polyurethane adhesives, the adhesion properties of which were obtained from T-peel tests on PVC/polyurethane adhesive/PVC joints. The addition of rosin as an internal tackifier increased the average molecular weight, more markedly in the TPU-Rs containing higher hard/soft segment ratios, but the elastic and viscous moduli decreased. An increase in the hard/soft segment ratio of the TPU-Rs retarded the kinetics of crystallization (which was determined by the soft segment content in the polyurethane), and increased the immediate T-peel strength in PVC/polyurethane adhesive/PVC joints (which was determined by the urethan-amide hard segments). Furthermore, addition of rosin to the polyurethanes decreased the final adhesion, although always reasonably high peel strength values were obtained.     

Stress relaxation in low‐shrink‐force polyolefin films

The morphology and stress relaxation of coextruded five‐layer LLDPE (linear low‐density polyethylene)/EVA (ethylene‐vinyl‐acetate) copolymer films were studied. Increasing VA (vinyl acetate) content in EVA causes a decrease of shrink tension in the films, which can be explained by a decrease in amount of crystallinity. The relaxation time spectrum of the coextruded crosslinked LLDPE/EVA films is similar to the relaxation time spectrum of crosslinked LLDPE film at room temperature. However, at elevated temperatures, an additional peak appears on the spectrum of coextruded film. The cause of this peak is temperature‐ and stress‐induced recrystallization of EVA during the relaxation test. This recrystallization was confirmed with DSC and wide angle X‐ray analysis. Polym. Eng. Sci. 44:1716–1720, 2004. © 2004 Society of Plastics Engineers.     

Corona discharge treatment of EVAs with different vinyl acetate contents

Four ethylene vinyl acetate (EVA) co-polymers with different vinyl acetate (VA) contents (9–20 wt%) were treated with corona discharge to improve their adhesion to polychloroprene (PCP) adhesive. The thermal properties of the EVAs decreased as their VA content increased, caused by a decrease in crystallinity. The elastic and viscous moduli of the EVAs decreased and the temperature and modulus at the cross-over between these moduli decreased with increasing VA content. Contact-angle measurements (water), infrared spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to analyse the surface modifications produced in the corona-discharge-treated EVAs. The corona discharge treatment produced improved wettability and created roughness and oxygen moieties on the EVA surfaces. The higher the VA content and the higher the corona energy, the more significant modifications were produced on the EVA surface. The VA content also affected the T-peel strength values of treated EVA/polychloroprene + isocyanate adhesive joints, as the values increased with increasing VA content. Mixed failure modes (interfacial + cohesive failure in the EVA) were obtained in the adhesive joints produced with corona discharge treated EVAs containing more than 9 wt% VA. The accelerated ageing of the joints did not affect the T-peel strength values, but the locus of failure in most cases became fully cohesive in the EVA, likely due to the higher extent of curing of the adhesive.     

Viscoelastic and adhesion properties of EVA/tackifier/wax ternary blend systems as hot-melt adhesives

Two types of wax were added to a ethylene vinyl acetate (EVA) copolymer/aromatic hydrocarbon resin (tackifier) blend in the molten state and the miscibility, viscoelastic and adhesion properties of ternary blends as hot-melt adhesives (HMAs) were investigated. Miscibility and viscoelastic properties were studied using differential scanning calorimetry (DSC), Brookfield viscometry and dynamic mechanical thermal analysis (DMTA), and their adhesion strength was determined in terms of single lap shear strength. DSC thermograms of both types of waxes showed their melting peaks in a similar region to that of EVA/tackfier blend. It was difficult to evaluate the miscibility of ternary blends using DSC because the melting peaks of the waxes overlapped with those of the EVA/tackifier blend, although the glass transition temperature (T _g) of the ternary blend systems slightly increased with increasing wax concentration. However, their storage modulus (E′) increased slightly and loss tangent (tan δ) showed different peaks when two types of wax were added to the EVA/tackifier blend. Therefore, the miscibility of EVA/tackifier blend altered with addition of waxes. In addition, their melt viscosity decreased with increasing wax concentration. Furthermore, the adhesion strength of the ternary blends decreased with increasing wax concentration, despite the increment of storage modulus. These results suggested that the ternary blends of EVA/tackifier/wax were heterogeneous.     

SURFACE MODIFICATIONS ON EVA TREATED WITH SULPHURIC ACID

In this study, treatment with sulphuric acid was used to increase the adhesion of an ethylene-vinyl acetate copolymer containing 20 wt% vinyl acetate (EVA20). The treatment with sulphuric acid improved the wettability of EVA20 due to thecreation of different oxygen and sulphonic acid moieties on the surface. The treatment also created cracks and heterogeneities on the EVA20 surface, and enhanced T-peel strength values of EVA20/polychloroprene adhesive+5 wt% isocyanate joints were obtained. The loci of failure of the joints were mixed, i.e. , adhesional and cohesive in the adhesive. Peel strength values of both as-received and sulphuric acid-treated EVA20/polychloroprene adhesive joints increased after ageing at 50°C and 95 wt% relative humidity for 72 because the complete cure of the adhesive was thereby was produced. The durability of the EVA20 treated with sulphuric acid was monitored between 15 min and 5 years. High peel strength values were obtained for times up to 61 days; the joints produced with the treated EVA20 five years after treatment showed lower peel strength value due to the creation of a weak boundary layer produced by reaction of the residual sulphuric acid on the surface with EVA20. On the other hand, different experimental variables in the treatment of EVA20 with sulphuric acid were considered. The optimum treatment conditions for EVA20 were obtained by immersion in highly concentrated sulphuric acid (96 wt%) for one minute followed by neutralisation with ammonium hydroxide.     

Surface modifications on eva treated with sulphuric acid

In this study, treatment with sulphuric acid was used to increase the adhesion of an ethylene-vinyl acetate copolymer containing 20 wt% vinyl acetate (EVA20). The treatment with sulphuric acid improved the wettability of EVA20 due to thecreation of different oxygen and sulphonic acid moieties on the surface. The treatment also created cracks and heterogeneities on the EVA20 surface, and enhanced T-peel strength values of EVA20/polychloroprene adhesive+5 wt% isocyanate joints were obtained. The loci of failure of the joints were mixed, i.e. , adhesional and cohesive in the adhesive. Peel strength values of both as-received and sulphuric acid-treated EVA20/polychloroprene adhesive joints increased after ageing at 50°C and 95 wt% relative humidity for 72 because the complete cure of the adhesive was thereby was produced. The durability of the EVA20 treated with sulphuric acid was monitored between 15 min and 5 years. High peel strength values were obtained for times up to 61 days; the joints produced with the treated EVA20 five years after treatment showed lower peel strength value due to the creation of a weak boundary layer produced by reaction of the residual sulphuric acid on the surface with EVA20. On the other hand, different experimental variables in the treatment of EVA20 with sulphuric acid were considered. The optimum treatment conditions for EVA20 were obtained by immersion in highly concentrated sulphuric acid (96 wt%) for one minute followed by neutralisation with ammonium hydroxide.     

Surface modifications of EVA copolymers induced by low pressure RF plasmas from different gases and their relation to adhesion properties

Two ethylene vinyl acetate (EVA) copolymers (12 and 20 wt% of vinyl acetate,VA, content) have been treated with low pressure RF plasmas from non-oxidizing gases (Ar, N₂) and oxidizing gases (air, a mixture of 4N₂: 6O₂ (v/v), O₂ and CO₂). The formation of polar moieties on both EVAs was more noticeable by treatment with plasmas from non-oxidizing gases than from oxidizing ones (the higher the reactivity, the lower the difference with respect to untreated EVA surfaces). The surface etching with the non-oxidizing plasmas, giving rise to a high roughness, depends on the wt% of VA in the composition of the copolymer because of the different resistances of VA (low) and PE (high) to the non-oxidizing plasma particles bombardment. The adhesion properties obtained using a polyurethane adhesive (PU) showed high T-peel strength values and adhesion failure in EVAs treated with plasmas from oxidizing gases, due to roughness produced causing mechanical interlocking of the adhesive. Lower T-peel strength values were obtained with non-oxidizing plasmas: the values for EVA12 being, in general, lower than those obtained for EVA20. The durability of the treated EVAs/PU adhesive joints after ageing in humidity and temperature was quite good.     

Ethylene vinyl acetate copolymer/halloysite nanotubes nanocomposites with enhanced mechanical and thermal properties

Ethylene vinyl acetate (EVA) nanocomposites filled with halloysite nanotubes (HNTs) were prepared by melt compounding. The homogenous dispersion of HNTs into the EVA matrix was evaluated by SEM and TEM analysis. The addition of HNTs does not influence on the phase separation structure and crystallinity of EVA nanocomposites. Due to the reinforcing effect of HNTs embedded in the EVA elastomer matrix, along with an increase of HNTs concentration, the improvement in tensile properties, by means of modulus at an elongation of 100% and tensile strength, was observed. It was found that tensile strength increased by 27% for EVA nanocomposite with 8 wt% of the HNTs. The values of elongation at break at low HNTs' loading increase and subsequently at higher loading are comparable to the neat EVA copolymer. The elastic deformability and reversibility of the EVA nanocomposites with different HNTs content was analyzed. The cyclic tensile tests showed that prepared nanocomposites have values of permanent set slightly higher than for neat EVA copolymer. Furthermore, the limiting oxygen index value for the EVA based nanocomposite with the highest HNTs content (8 wt%) increased from 19.5 to 24.8%. The results show, that thermo-oxidative stability were improved by the incorporation of HNTs into EVA copolymer matrix.     

Ethylene vinyl acetate and ethylene vinyl alcohol copolymer for thermal spray coating application

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.