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     

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     

Aspects of miscibility in poly(vinyl chloride)/epoxidized natural rubber blends. Part II: Dynamic mechanical properties

Miscibility in poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blends was further investigated by means of dynamic mechanical analysis. The single glass transition temperature shown by the blends supported earlier observations of miscibility Furthermore, observed synergism in storage modulus has again reaffirmed the miscibility of these blends. A critical examination of the damping peaks at various compositions again revealed the microheterogeneous nature of the blends. Some theories relating glass transition temperature and modulus with miscibility were also used to examine miscibility. Agreement of the results with theories proposed by Gordon—Taylor and Kleiner has provided a further insight into the miscible nature of PVC/ENR blends.     

Elongational viscosity for miscible and immiscible polymer blends. I. PMMA and AS with similar elongational viscosity

The effects of miscibility and blend ratio on uniaxial elongational viscosity of polymer blends were studied by preparing miscible and immiscible samples at the same composition by using poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-co-styrene) (AS). Miscible polymer blend samples for the elongational viscosity measurement were prepared by using three steps: solvent blends, cast film, and hot press. A phase diagram of blend samples was made by visual observation of cloudiness. Immiscible blend samples were prepared by maintaining the prepared miscible samples at 200°C, which is higher than cloud points using a LCST (lower critical solution temperature) phase diagram. The phase structure of immiscible blends was observed by an optical microscope. The elongational viscosity of all samples was measured at 145°C, which is lower than the cloud-point temperature at all blend ratios. The elongational viscosity of PMMA and AS was similar to each other. The strain-hardening property of miscible blends in the elongational viscosity was only slightly influenced by the blend ratio, and this was also the case with immiscible blends. The strain-hardening property was only slightly influenced, whether it was miscible or immiscible at each blend ratio. Polydispersity in molecular weight for blend samples was not changed by GPC (gel permeation chromatography) analysis. Almost no change in the polydispersity of the molecular weight for blends and the similarity of elongational viscosity between PMMA and AS resulted in little influence of the blend ratio and miscibility on the strain-hardening property. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 757–766, 1999     

Miscibility and adhesive properties of EVA‐based hot‐melt adhesives. II. Peel strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that were made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of the typical miscibility types and investigated their peel strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of peel strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the storage modulus of the blends whose curves tended to move toward higher temperature as tackifier content of blends increased when blend components were miscible as well as their maximum values of tan δ, or glass transition temperatures. It was characteristic for peel strength that there existed second peaks on peel strengths curves at ～ 100°C, which adhesive tensile strengths for the blends did not have. In terms of relationship between miscibility and HMA performances, we suggest that there are several factors other than miscibility that affect absolute values of peel strength more directly than miscibility; this idea has to be investigated further in the a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 726–735, 2002     

Miscibility of blends of epoxidized natural rubber and poly(ethylene-co-acrylic acid)

The blends of epoxidized natural rubber (50 mol %) (ENR) and poly(ethylene-co-acrylic acid) (PEA) (6 wt %) are demonstrated to be partially miscible up to 50% by weight of PEA and completely miscible beyond this proportion. The miscibility has been confirmed by a DSC study which exhibits a single second-order transition (T_g) for the 30 : 70 and 50 : 50 (ENR : PEA) blends. For the 70 : 30 (ENR : PEA) blend, the T_g's shift toward an intermediate value but do not merge to form a single T_g, making the blend partially miscible. The miscibility has been assigned to the esterification reaction between – OH groups formed in situ during melt blending of ENR and – COOH groups of PEA. The occurrence of such reactions have been confirmed by UV and IR spectroscopic studies. The existence of a single phase of the blends beyond 50 wt % of PEA has been shown by SEM studies. © 1995 John Wiley & Sons, Inc.     

Rheological behavior of reactive blending of epoxidized natural rubber with cassava starch and epoxidized natural rubber with natural rubber and cassava starch

Epoxidized natural rubbers (ENR‐25 and ENR‐45) were prepared using the performic epoxidation method. Two‐component (ENR–cassava starch) and three‐component (ENR–NR–cassava starch) blends were prepared. ENR‐25 and ENR‐45 were blended with various quantities of gelatinized cassava starch in the latex state. The pure ENR exhibited lower shear stress and shear viscosity than those of the blends with cassava starch. Furthermore, the shear stress and shear viscosity were increased with an increase in the cassava starch concentration. The chemical interaction between the epoxide groups in the ENR and the hydroxyl groups in the cassava starch molecules might be the reason for the increasing trends of the shear stress and shear viscosity. The blends are classified as compatible blends because of the strong chemical bonding between different phases. SEM micrographs were used to clarify the compatibility. Power law behavior with pluglike flow profiles was observed for all sets of ENR–NR–cassava starch blends. Very low power law index values (<0.34) and highly pseudoplastic fluid behavior were also observed. The log additive rule was applied to plots of zero shear viscosity (consistency index) and the shear viscosity versus the concentration of ENR‐25. Positive deviation blending was observed, which indicates compatible blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1752–1762, 2004     

Miscibility of poly(α-methyl siyrene-co-acrylonitrile) with polyacrylates and polymethacrylates

A copolymer formed from 30 percent acrylonitrile and 70 percent α methyl styrene by weight, or αMSAN, has been examined for miscibility in blends with various polyacrylates and polymethacrylates. None of the polyacrylates or poly(vinyl acetate) were miscible with α-MSAN at room temperature or above. The methyl and ethyl esters of the polymethacrylate series (PMMA, PEMA) proved to be miscible with α MSAN, but none of the higher homologues were miscible under these conditions. Blends of both PMMA and PEMA with α MSAN exhibited lower critical solution temperatures. The observed cloud points decreased as PMMA molecular weight increased up to 10⁵ where kinetic effects caused an apparent reversal of this trend. Atactic PMMA interacts more strongly with αMSAN than does either isotactic PMMA or atactic PEMA. These structural effects are compared with similar trends found in other systems.     

Study on the milling behavior of chloroprene rubber blends with ethylene–propylene–diene monomer rubber,polybutadiene rubber,and natural rubber

The viscoelastic properties of the blends of chloroprene rubber (CR) with ethylene–propylene–diene monomer rubber (EPDM), polybutadiene rubber (BR), and natural rubber (NR) at different temperature were studied using rubber processing analyzer (RPA). Mooney viscosities of compounds were measured and tight milling and sheeting appearance were observed on a two‐roll mill. The results showed that Mooney viscosities and the elastic modulus of the blends decreased with the increase of the temperature from 60 to 100°C. And the decreasing trends of pure CR, pure NR, and CR/NR blend compounds were more prominent than that of pure EPDM, pure BR, CR/EPDM, and CR/BR blend compounds. For CR/EPDM blend compounds, the decreasing trend became slower with the increase of EPDM ratio in the blend. Compared with pure CR, pure NR and CR/NR blend compounds, pure EPDM, pure BR compounds, and the blend compounds of CR/EPDM and CR/BR showed less sensibility to temperature and they were less sticky to the metal surface of rolls and could be kept in elastic state at higher temperature, easy to be milled up and sheeted. At the same blend ratio and temperature, the property of tight milling of the blends decreased in the sequence of CR/EPDM, CR/BR, and CR/NR. With the increase of EPDM, BR, or NR ratio in CR blends, its property of tight milling was improved. POLYM. COMPOS., 28:667–673, 2007. © 2007 Society of Plastics Engineers     

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     

Miscibility and adhesive properties of ethylene vinyl acetate copolymer (EVA)‐based hot‐melt adhesives. I. Adhesive tensile strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that are made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of typical miscibility types and measured their adhesive tensile strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of adhesive tensile strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the glass transition temperature (T_g) of the blends that became higher as tackifier content of blends increased when blend components were miscible. In terms of HMA performances, we suggest that factors other than miscibility affect absolute values of adhesive tensile strength more directly than miscibility; this idea has to be investigated further in a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 719–725, 2002     

Miscibility of chitosan–hydroxyethylcellulose blends in aqueous acetic acid solutions at 35°C

The miscibility of blends of chitosan and hydroxyethylcellulose in a 2% acetic acid solution was studied by viscometry, densitometry, and refractometry at 35°C. The data suggest that the blends were completely miscible in all proportions. Further, the membranes were fabricated from concentrated blend solutions. The solid‐state compatibility of the blends was confirmed by scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1996–1998, 2005     

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.     

Blending of natural rubber with linear low-density polyethylene

Blends of natural rubber (NR) with linear low-density polyethylene (LLDPE) were prepared by melt blending of the materials in a plasticorder mixer at various temperatures around the melting point of LLDPE and at various mixing rates. The optimum processing conditions were a temperature of about 135°C and a mixing rate of 55 rpm. The tensile properties, stress and strain, of the blend had improved significantly with the addition of liquid natural rubber (LNR) into the blend. For blends with compositions around 50% NR, about 10–15% LNR produced the most significant improvement in the physical properties. Welldispersed plastic particles in a rubber matrix were strongly indicated in these samples. Scanning electron micrographs (SEM) of the samples also indicated an increase in the homogeneity of the mixes with the addition of LNR. A single glass transition temperature of about?55°C for the blend was observed via dynamic mechanical analysis (DMA). Interfacial linking between the NR and LLDPE phases was attributed to the presence of active groups on the polyisoprene chain of LNR, which induced the interphase reaction between the NR and LLDPE phases. © 1995 John Wiley & Sons, Inc.     

Dextran/poly(acrylic acid) mixtures as miscible blends

Bioartificial polymeric materials based on blends of dextran and poly(acrylic acid) were prepared in form of films and characterized in order to evaluate the miscibility of the natural component with the synthetic one. Films with different composition ratios were prepared by solution casting and analyzed by dynamic mechanical-thermal analysis, differential scanning calorimetry, and scanning electron microscopy. The obtained results indicate that dextran is miscible with poly(acrylic acid). The miscibility was mainly ascertained on the bases of the occurrence of a single composition-dependent glass transition temperature in each blend and also on the bases of the transparency and homogeneity of the films. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2089–2094, 1997     

New miscible blends composed of polysulfone and poly(1-vinylpyrrolidone-co-acrylonitrile) copolymers and their phase behavior

The miscibility of polysulfone, PSf, blend with poly(1-vinylpyrrolidone), PVP, and that of PSf blend with poly(1-vinylpyrrolidone-co-acrylonitrile) copolymers, P(VP-AN), containing various amount of VP were explored. Even though PSf did not formed miscible blends with PVP when both components had high molecular weight, it formed miscible blend with PVP by decreasing molecular weight of PVP. PSf also formed homogeneous mixtures with P(VP-AN) containing AN from 2 to 16 wt%. These miscible blends underwent phase separation on heating caused by LCST-type (lower critical solution temperature-type) phase behavior. The phase separation temperature of miscible blends first increases with AN content, goes through a maximum centered at about 8 wt% AN. Interaction energies of binary pairs involved in blends were evaluated from the observed phase boundaries using the lattice-fluid theory. The decline of the contact angle between water and blend film by increasing P(VP-AN) content in blend indicated that the hydrophobic properties of PSf could be improved by blending with P(VP-AN) copolymers.     

Dichlorocarbene modification of natural rubber and its role as a modifier in blends of natural rubber and hydrogenated nitrile rubber

Dichlorocarbene modification of natural rubber (NR) carried out by alkaline hydrolysis of chloroform in presence of cetyl trimethyl ammonium bromide as phase‐transfer catalyst was investigated. Extent of chemical reaction was characterized by estimation of chlorine content and FTIR studies. Rate of dichlorocarbene addition depends on the time and temperature of reaction. Reaction carried out at 60°C for 2 h yielded a material with a chlorine content of 15%. Chemical modification of NR was accompanied by introduction of chlorine through cyclopropyl ring to the main chain of NR as revealed from FTIR studies. As level of chlorination increased, the physical nature of NR changed from a soft flexible state to a hard nontacky form. Blends of NR with hydrogenated nitrile rubber (HNBR) containing three to seven parts of dichlorocarbene‐modified NR (DCNR) of chlorine content 15% could be prepared by conventional mill mixing. Incorporation of DCNR into blends of NR and HNBR promoted polar interaction between the chlorine segments and acrylonitrile segments of the blend as shown from the shift in characteristic IR absorption peaks and shift in T_g from DSC studies. As a consequence, DCNR acted as an interface modifier in blends of NR and HNBR. Blends of NR and HNBR containing DCNR showed a considerable improvement in cure behavior, physical properties, and ageing characteristics in oil, ozone, and high temperature compared to pure blends of NR and HNBR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4401–4409, 2006     

Effect of bisphenol A on the miscibility,phase morphology,and specific interaction in immiscible biodegradable poly(ε‐caprolactone)/poly(L‐lactide) blends

We have investigated the enhancement in miscibility, upon addition of bisphenol A (BPA) of immiscible binary biodegradable blends of poly(ε‐caprolactone) (PCL) and poly(L ‐lactide) (PLLA). That BPA is miscible with both PCL and PLLA was proven by the single value of T_g observed by differential scanning calorimetry (DSC) analyses over the entire range of compositions. At various compositions and temperatures, Fourier transform infrared spectroscopy confirmed that intermolecular hydrogen bonding existed between the hydroxyl group of BPA and the carbonyl groups of PCL and PLLA. The addition of BPA enhances the miscibility of the immiscible PCL/PLLA binary blend and transforms it into a miscible blend at room temperature when a sufficient quantity of the BPA is present. In addition, optical microscopy (OM) measurements of the phase morphologies of ternary BPA/PCL/PLLA blends at different temperatures indicated an upper critical solution temperature (UCST) phase diagram, since the ΔK effect became smaller at higher temperature (200°C) than at room temperature. An analysis of infrared spectra recorded at different temperatures correlated well with the OM analyses. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1146–1161, 2006     

Thermal fractionation and properties of different polyethylene/wax blends

The influence of paraffin‐wax type and content on the properties of its blends with HDPE, LDPE, and LLDPE was investigated. Melt‐mixing of HDPE with wax gave rise to completely miscible blends for both 10 and 20% wax contents. A wax content of 30% gave rise to a partially miscible blend. These observations were supported by the thermal fractionation (stepwise cooling) results. Melt‐mixing of LDPE with hard paraffin wax gave rise to a partially miscible blend for all wax contents investigated, while complete miscibility was observed for the 10% oxidized hard paraffin wax containing blend. Complete miscibility was observed for all the LLDPE/A1 wax blends, with A1 wax as an oxidized hard paraffin wax. This indicates possible cocrystallization of this wax with LLDPE, which was also evident from the thermal fractionation curves. LLDPE blends with hard paraffin wax were, however, partially miscible for all wax contents. All the observations were supported by the surface free energy results. It is further clear from the thermal fractionation results that the presence of wax changed the crystallization behavior of LDPE and LLDPE. Changes in the tensile properties are explained in terms of the miscibility and proposed morphologies of the blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2225–2236, 2007