Miscibility and PSA Performance of Acrylic Copolymer and Tackifier Resin Systems

The influence of miscibility of an acrylic PSA and several tackifier resin systems upon PSA performance was investigated. When the acrylic copolymer and the resins were blended in various proportions, three types of mixing state were found: miscible system, partially miscible system and immiscible system. In the case of miscible systems, PSA performance (tack, peel strength and shear resistance) depended upon the viscoelastic properties of the PSA. In the case of completely immiscible systems, the above PSA performance depended primarily upon the viscoelastic properties of a continuous matrix phase, and the separated resin phase acted as a kind of filler. In the case of partially miscible systems, the PSA performance changed discontinuously at the resin concentration where phase separation occurred. It suggests that the phase structure of a PSA greatly influences the PSA's performance.     

Miscibility and fracture energy of probe tack for acrylic pressure-sensitive adhesives: acrylic copolymer/tackifier resin systems

The relationship between the miscibility of acrylic pressure-sensitive adhesive (PSA) and the fracture energy (W) (Jm⁻²) of the probe tack was investigated, wherein the master curve of W was compared with that of the maximum force (σ_max) (gf) of the probe tack. It was ascertained that W of acrylic PSA was closely related to the miscibility between the components (acrylic copolymer and tackifier resin). In the case of the miscible blend system, the master curve of W shifted toward the lower rate side and, at the same time, the magnitude decreased as the tackifier resin content increased. The degree of the shift of W was extremely smaller than that of σ_max. In the case of the immiscible blend system, the master curve of W remarkably decreased as the tackifier resin content increased, which suggests the fact that W of the PSA depended on the dynamic mechanical properties of the matrix phase and that the resin-rich phase acted as a kind of filler, thus reducing the practical performance. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 581–587, 1998     

Miscibility and pressure‐sensitive adhesive performances of acrylic copolymer and hydrogenated rosin systems

Relationship between the miscibility of pressure‐sensitive adhesives (PSAs) acrylic copolymer/hydrogenated rosin systems and their performance (180° peel strength, probe tack, and holding power), which was measured over a wide range of time and temperature, were investigated. The miscible range of the blend system tended to become smaller as the molecular weight of the tackifier increased. In the case of miscible blend systems, the viscoelastic properties (such as the storage modulus and the loss modulus) shifted toward higher temperature or toward lower frequency and, at the same time, the pressure‐sensitive adhesive performance shifted toward the lower rate side as the T_g of the blend increased. In the case of acrylic copolymer/hydrogenated rosin acid systems, a somewhat unusual trend was observed in the relationship among the phase diagram, T_g, and the pressure‐sensitive adhesive performance. T_g of the blend was higher than that expected from T_gs of the pure components. This trend can be due to the presence of free carboxyl group in the tackifier resin. However, the phase diagram depended on the molecular weight of the tackifier. The pressure‐sensitive adhesive performance depended on the viscoelastic properties of the bulk phase. A few systems where a single T_g could be measured, despite the fact that two phases were observed microscopically, were found. The curve of the probe tack of this system shifted toward a lower rate side as the T_g increases. However, both the curve of the peel strength and the holding power of such system did not shift along the rate axis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 651–663, 1999     

Rheological analysis of the adhesion surface with a scanning probe microscope (SPM)

The frictional forces between pressure sensitive adhesives (PSAs), including rosin tackifier resin, and a probe tip were measured with scanning probe microscopy (SPM). A peak that appeared in the scanning rate-frictional force curve shifted to a lower scanning rate with decrease in temperature. The frictional force reflects rheological behavior of the PSA. In the case of the miscible system, the tendency of a peak to shift to a lower scanning rate was observed with increase in tackifier content; however, in the case of the immiscible system, no remarkable shift was observed. The frictional force is influenced by viscoelastic properties of the PSA, which systematically changed with miscibility. The high-scanning rate resulted in the interfacial failure on the surface, while the low-scanning rate resulted in the cohesion failure.     

Effects of miscibility and viscoelasticity on shear creep resistance of natural‐rubber‐based pressure‐sensitive adhesives

Natural rubber (NR) was blended in various ratios with 29 kinds of tackifier resins. Miscibilities of all the blend systems were illustrated as phase diagrams. From these blend systems, we selected 8 systems having typical phase diagrams (completely miscible, immiscible, lower critical solution temperature [LCST] types) and carried out measurements of shear creep resistance (holding power). Holding time was recorded as required time for the pressure‐sensitive adhesive (PSA) tape under shear load to completely slip away from the adherend. Holding time of miscible PSA systems tended to decrease as the tackifier content increased. This is attributable to a decrease in plateau modulus of the PSA with increasing tackifier content. There was rather large difference in holding time by tackifier among the miscible PSA systems; the reason for this is also considered to be a difference in plateau modulus. Holding time of an immiscible PSA system scarcely changed by tackifier content. But in another immiscible system, holding time tended to increase with increasing tackifier content. In fact, in the case of immiscible PSAs, the effect of tackifier content on holding time was different from tackifier to tackifier. This may be caused by difference in extent of phase separation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1535–1545, 2000     

Surface Property and Compatibility of Poly(styrene-isoprene-styrene) Triblock Copolymer/Tackifier Blend System

The frictional forces between pressure sensitive adhesives (PSAs) and a probe tip were measured with a scanning probe microscopy (SPM). A peak appeared in the scanning rate-frictional force curve shifted to a lower scanning rate with decreasing temperature. In the case of the miscible system of isoprene matrix of SIS base polymer, the tendency of a peak to shift to a lower scanning rate was observed with increasing tackifier content; however, in the case of the immiscible system of styrene domain of SIS base polymer, no remarkable shift was observed. The frictional force is influenced by viscoelastic properties of the PSA which systematically changed with miscibility.

In this study, it is aimed to clarify the correlation between the observation of phase structure and the behavior of surface rheology by using two kinds of tackifiers that have different miscibility with the polyisoprene phase or the polystyrene phase of SIS triblock copolymer.     

PC部分相容和不相容体系的研究进展

对以聚碳酯／聚对苯二甲酸二丁酯(PC／PBT)为代表的PC部分相容体系以及聚碳酸酯／聚乙烯(PC／PE)为代表的PC不相容体系的国内外研究情况进行了评述。主要包括PC合金的相容性,PC合金的结构形态与性能的关系等。并提出了如何测定酯交换反应程度的设想。     

Water-based polymers as pressure-sensitive adhesives—viscoelastic guidelines

Water-based polymers have been widely used as pressure-sensitive adhesives (PSAs). This article addresses the fundamental viscoelastic parameters that govern PSA performance. The viscoelastic behavior of polymers before and after resin tackification is investigated. Commercial acrylic, CSBR, natural rubber emulsion polymers, and low M_W petroleum-based hydrocarbon resins with various softening points are used to demonstrate the tackification effects. Basic guidelines for selecting the appropriate polymer/resin system to achieve the target performance are given. © 1995 John Wiley & Sons, Inc.     

Phase behavior of ternary polymer blends

The effect of varying interaction parameters on the phase diagrams of ternary polymer blends was explored by simulating spinodals through use of the Flory-Huggins lattice theory. Results indicate that miscibility is favored for the case of ternary mixtures of marginally miscible or marginally immiscible pairs where all pair interactions are nearly athermal. Miscibility is restricted for asymmetric ternary blends when one of the polymer pairs is either strongly miscible or strongly immiscible. For symmetric blends of partially immiscible pairs, both two-phase and three-phase miscibility gaps are predicted.     

The Effect of Phase Structure on the Tribological Properties of PA66/HDPE Blends

Summary: In this paper, immiscible, partially miscible and miscible blends of polyamide 66 (PA66) and high density polyethylene (HDPE) were obtained by changing compatibilizer concentrations. Mechanical and tribological properties of materials were tested. It was found that the addition of compatibilizer greatly improved the mechanical properties of PA66/HDPE blends. The wear of PA66/HDPE blends was strongly affected by the phase structure. The best blend for lower friction coefficient and higher wear resistance was the blend with a miscible structure, which significantly improved the tribological properties of PA66 and HDPE. SEM investigations on the worn surface and the steel counterface indicated that, for the immiscible and partially miscible blend systems, the dispersed HDPE particles were pulled out from the worn surfaces during sliding because of the poor adhesion between HDPE and PA66, while this was not observed in the miscible blend system.

SEM micrograph of the worn surface formed by PA66/HDPE blend without HDPE‐g‐MAH.     

Thermal and rheological properties of mLLDPE/LDPE blends

The thermal and rheological properties of two types of metallocene‐catalyzed linear low‐density PEs (mLLDPEs) and two LDPEs, as well as their blends, were studied using differential scanning calorimeter (DSC) measurements and rheometry. The DSC results showed that the mLLDPE‐1 based on the hexene comonomer is immiscible with both LDPEs in crystalline states, whereas the mLLDPE‐2 based on the octene comonomer is miscible with the LDPEs. This suggests that increasing the length of short chains in mLLDPEs can promote the miscibility of mLLDPE/LDPE blends. The linear viscoelastic properties confirmed the immiscibility of the mLLDPE‐1 with the LDPEs in the molten state, and the miscibility of mLLDPE‐2 with LDPEs. In addition, the Palierne [1] emulsion model provided good predictions of the linear viscoelastic data for both miscible and immiscible PE blends. However, as expected, the low‐frequency data showed a clear influence of the interfacial tension on the elastic modulus of the blends for the immiscible blends. POLYM. ENG. SCI., 45:1254–1264, 2005. © 2005 Society of Plastics Engineers     

Miscibility and shear creep resistance of acrylic pressure-sensitive adhesives: Acrylic copolymer and tackifier resin systems

The miscibility between an acrylic copolymer and a tackifier resin was investigated in terms of phase diagrams, glass transition temperatures (T_g's), and dynamic mechanical properties of blends. Shear creep resistance (holding power, t_b) of the blends was measured as a function of both temperature and stress (σ₀) in order to obtain the master curves. It was found that the shear creep resistance of the pressure-sensitive adhesives (PSAs) was closely related to the miscibility between the components and viscoelastic properties of the blends. The master curve of the miscible blends shifts toward a longer time scale as the amount of tackifier resin in the blend is increased as a result of the modification of the bulk properties, and their behavior greatly depends on the glass transition temperature (T_g) and storage modulus (G′) of the blends. However, the master curve of immiscible blends where two phases exist in the system does not shift greatly toward a longer time scale, because T_g and the storage modulus of the blend do not change greatly. © 1995 John Wiley & Sons, Inc.     

Dynamic mechanical properties and adhesive strengths of epoxy resins modified with liquid rubber. I. Modification with ATBN

The dynamic mechanical properties and the adhesive strengths of Epikote 828 and Epikote 828-ATBN blend systems were investigated. The ATBN blend systems were proved to be completely incompatible with the dynamic mechanical measurement and also fitted well with Takayanagi's model which was designed for completely incompatible two-phase systems. The epoxy resin had a nonreacted part when cured at room temperature. The blending of ATBN reduced the nonreacted part of the epoxy resin, and made contributions to the adhesive strengths. In the case of tensile test of crosslap specimens using aluminium as adherends, the adhesive strengths of ATBN blend systems were almost 1.5-fold of those of epoxy resin without blending of ATBN. As for wood adherends, the maximum of the adhesive strengths was found at 60°C for epoxy resin without blending of ATBN, and at 0°C for ATBN blend systems. The facts meant that there were mutual interactions between the adhesive strengths and the viscoelastic behavior of the adhesive polymers in the two-phase systems as observed in completely miscible polymer blends. There was not pronounced distinction between epoxy resins without blending of ATBN and ATBN blend system, as to the shear adhesive strengths.     

Miscibility between natural rubber and tackifiers. II. Phase diagrams of the blends of natural rubber and petroleum resins

Natural rubber (NR) was blended in various ratios with 12 kinds of tackifiers that were prepared from petroleum. The blends were heated to various temperatures (20–120°C) to investigate their miscibility. The blends were visually observed for transparency or opacity at each temperature and further observed under an optical microscope for any existence of phase-separated structure. Miscibility of the blends is illustrated as phase diagrams in this article. NR/aliphatic resin systems and NR/aliphatic-aromatic copolymer systems showed phase diagrams of the lower critical solution temperature type, wherein the blends turned faintly cloudy over the binodal curves. The NR/hydrogenated petroleum resin system also showed a phase diagram of the lower critical solution temperature type. The miscible range of a blend system tends to become smaller as the molecular weight of a tackifier increases. Resins prepared by polymerization of pure aromatic monomers were completely immiscible with NR. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 221–229, 1998     

Poly(vinylidene fluoride)–acrylic rubber partially miscible blends: Phase behavior and its effects on the mechanical properties

A phase diagram of poly(vinylidene fluoride) (PVDF) and acrylic rubber (ACM) was plotted, and the effects of the extent of miscibility on the mechanical properties of the polymer blends were examined. A compressible, regular solution model was used to forecast the phase diagram of this blend. The model prediction, the lower critical solution temperature (LCST) over the upper critical solution temperature (UCST), was done qualitatively according to the experimentally determined phase diagram by differential scanning calorimetry (DSC), optical microscopy, and rheological analysis. These experimental methods showed that this system was miscible in ACM‐rich blends (>50% ACM) and partially miscible in PVDF‐rich blends. A wide‐angle X‐ray diffraction study revealed that PVDF/ACM blends such as neat PVDF had a characteristic α‐crystalline peak. The partially miscible blends displayed up to 350% elongation at break; this was a significant increment of this parameter compared to that of neat PVDF(20%). However, the miscible blends showed elongation of up to 1000% [again, a remarkable increase compared to chemically crosslinked ACM (220%)] and displayed excellent mechanical properties and tensile strength and a large elongation at break. For the miscible and partially miscible blends, two different mechanisms were responsible for this improvement in the mechanical properties. It was suggested that in the partially miscible blends, the rubbery depletion layer between the spherulite and the conventional rubber cavitations mechanism were responsible for the increase in the elongation at break, whereas for the miscible blends, the PVDF spherulite acted as a crosslinking junction. The stretched part of the tensile samples in the partially miscible blends showed characteristic β‐crystalline peaks in the Fourier transform infrared spectra, whereas that in the miscible blends showed α‐crystalline peaks. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1247‐1258, 2013     

Mechanism for the action of tackifying resins in pressure-sensitive adhesives

In a study of pressure-sensitive adhesives prepared from mixtures of natural rubber and three different tackifying resins, it was shown that a tackifying resin may form either one- or two-phase systems with natural rubber. Measurements of the viscoelastic properties of the adhesives show that the effect of tackifying resins is to modify the viscoelastic properties so that the adhesive performance in bonding and unbonding is improved. It is suggested that a two-phase system is not necessary for good tack, and a theory based on a two-phase system cannot adequately explain the rate dependence of tack tests. Tack measured by the probe test is shown to be dependent upon a balance between the viscoelastic properties and the transition temperature of the adhesives. This theory is used to explain the effect of contact time, withdrawal speed, and resin softening point on the tack of adhesives.     

Effects of miscibility on probe tack of natural-rubber-based pressure-sensitive adhesives

Natural rubber (NR) was blended in various ratios with 29 kinds of tackifier resins, which were prepared from rosin, terpenes, and petroleum. Miscibilities of all the blend systems were illustrated as phase diagrams in our previous articles. From these blend systems, we selected 7 systems having typical phase diagrams [completely miscible, completely immiscible, and lower critical solution temperature (LCST) types] and carried out measurements of probe tack. Probe tack values were measured at various rates of separation and temperatures to obtain master curves. In the case of miscible pressure sensitive adhesives (PSAs) at the condition of measurement, the peak position in the master curve of probe tack shifted to the lower velocity (higher temperature) as the tackifier content increased. On the contrary, immiscible PSAs had much smaller probe tack values than miscible ones and did not give manifest shift of peaks. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 771–776, 1998     

Studies on the characteristics of microphase separation and stabilization of interphase for blended systems of high performance polymers

In this report, we review and discuss the results of our recent studies on the characteristics of microphase separation behavior and interphase stabilization for high performance polymer blends. The blends investigated include crystalline/crystalline polymers, crystalline/amorphous polymers, liquid crystalline polymer/thermoplastics, and amorphous/amorphous thermoplastics or thermosetting systems. Most of the blends are either immiscible or partially miscible, and are thermodynamically unstable or meta-stable systems. The macro-properties of these blends are controlled by many factors such as the miscibility, phase morphology and structure, crystallinity, kinetics of crystallization or phase separation processing, and interfacial adhesion of the components. Among these, the microphase and interfacial structures are the most significant factors influencing the ultimate properties of the blends. In order to obtain relatively stable blends, formation of semi-IPN in either the bulk or interphase, and/or the occurrence of crosslinking, transesterification and physical entanglement in the interfacial region will be profitable to the stabilization of the blending systems.The project supported by FORD and NSFC No. 09415312     

Morphology and rheological properties of polypropylene/reactive elastomer blends

The relation of morphology to the linear viscoelastic properties for polymer blends consisting of an inert polypropylene and an elastomeric dispersed phase, made of two miscible copolymers, EVA and EMA, was investigated. The rheological properties of the elastomeric phase were modified by crosslinking in presence of an organometallic catalyst. The activation energy for the transesterification reaction taking place between EVA and EMA has been determined by following the increases of the complex viscosity with time and temperature. The Palierne model has been used to describe the linear viscoelastic behavior of the blends, and to estimate the interfacial tension between the immiscible components. The model was shown to describe relatively well the linear viscoelastic properties of reactive and nonreactive blends containing 30% or less elastomer. In parallel, the morphology of reactive and nonreactive blends (i.e. without catalyst in the elastomeric phase), before and after rheological experiments, has been determined using scanning electron microscopy. The size of the dispersed elastomeric particles for reactive blends prepared using an internal mixer was found to be, in most cases, much smaller than that for nonreactive blends.     

Immiscibility–miscibility phase transitions in blends of poly(L‐lactide) with poly(methyl methacrylate)

BACKGROUND: The nature of phase transitions and apparently irreversible phase homogenization upon heating in blends of biodegradable poly(L ‐lactide) (PLLA) with poly(methyl methacrylate) (PMMA) were proven using differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy and ¹H NMR spectroscopy. The complex phase behaviour in this blend system is puzzling and is a matter of debate; this study attempts to clarify the true nature of the phase behaviour. RESULTS: A PMMA/PLLA blend is immiscible at ambient temperature but can become miscible upon heating to higher temperatures with an upper critical solution temperature (UCST) at 230 °C. The blends, upon rapid quenching from the UCST, can be frozen into a quasi‐miscible state. In this state, the interaction strength was determined to be χ₁₂ = ? 0.15 to ? 0.19, indicating relatively weak interactions between the PLLA ester and PMMA acrylic carbonyl groups. CONCLUSION: The absence of chemical exchange reactions above the UCST and phase reversibility back to the original phase separation morphology, assisted by solvent re‐dissolution, in the heat‐homogenized PLLA/PMMA blend was shown. Verification of UCST behaviour, phase diagrams and solvent‐assisted phase reversibility were experimentally demonstrated in PMMA/PLLA blends. Copyright © 2008 Society of Chemical Industry