Miscibility of copolycarbonate blends with poly(styrene-co-acrylonitrile) copolymer and their interaction energies

The phase behavior of dimethyl polycarbonate-tetramethyl polycarbonate (DMPC-TMPC) blends with poly(styrene-co-acrylonitrile) copolymers (SAN) and the interaction energies of binary pairs involved in blend has been explored. DMPC-TMPC copolycarbonates containing 60 wt% TMPC or more were formed miscible blends with SAN containing limited amounts of AN. The miscibility of copolycarbonate with SAN decreases as the DMPC content increases. The miscible blends showed the LCST-type phase behavior or did not phase separate until thermal degradation. The binary interaction energies involved in the miscible blends were calculated from the phase boundaries using the lattice-fluid theory combined with binary interaction model. The phenyl ring substitution with methyl groups did not lead to interactions that are favorable for miscibility with polyacrylonitrile (PAN). The interaction energies of the polycarbonates blends with SAN copolymers as a function of AN content were obtained. It was revealed that the incline of the number of methyl groups on the phenyl rings of bisphenol-A unit acts favorably for the miscibility with SAN copolymer when SAN contains less than about 30 wt% AN and shifts the most favorable interaction to the low AN content.     

Viscoelastic properties of blends of poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile) having various acrylonitrile contents

Dynamic viscoelastic properties of blends of poly(methyl methacrylate) (PMMA) and poly(styrene‐co‐acrylonitrile) (SAN) with various AN contents were measured to evaluate the influence of SAN composition, consequently χ parameter, upon the melt rheology. PMMA/SAN blends were miscible and exhibited a terminal flow region characterized by Newtonian flow, when the acrylonitrile (AN) content of SAN ranges from 10 to 27 wt %. Whereas, PMMA/SAN blends were immiscible and exhibited a long time relaxation, when the AN content in SAN is less than several wt % or greater than 30 wt %. Correspondingly, melt rheology of the blends was characterized by the plots of storage modulus G′ against loss modulus G″. Log G′ versus log G″ plots exhibited a straight line of slope 2 for the miscible blends, but did not show a straight line for the immiscible blends because of their long time relaxation mechanism. The plateau modulus, determined as the storage modulus G′ in the plateau zone at the frequency where tan δ is at maximum, varied linearly with the AN content of SAN irrespective of blend miscibility. This result indicates that the additivity rule holds well for the entanglement molecular weights in miscible PMMA/SAN blends. However, the entanglement molecular weights in immiscible blends should have “apparent” values, because the above method to determine the plateau modulus is not applicable for the immiscible blends. Effect of χ parameter on the plateau modulus of the miscible blends could not be found. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Investigation on the miscibility of the blends of poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile)

The miscibility was investigated in blends of poly(methyl methacrylate) (PMMA) and styrene‐acrylonitrile (SAN) copolymers with different acrylonitrile (AN) contents. The 50/50 wt % blends of PMMA with the SAN copolymers containing 5, 35, and 50 wt % of AN were immiscible, while the blend with copolymer containing 25 wt % of AN was miscible. The morphologies of PMMA/SAN blends were characterized by virtue of scanning electron microscopy and transmission electron microscopy. It was found that the miscibility of PMMA/SAN blends were in consistence with the morphologies observed. Moreover, the different morphologies in blends of PMMA and SAN were also observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Blends of imidized acrylic polymers with SAN copolymers and with PVC

A series of imidized acrylic polymers of varying structural composition generated by reaction of methylamine with poly(methyl methacrylate) were blended with a range of styrene/acrylonitrile or SAN copolymers (0–33% AN) and with poly(vinyl chloride). On the basis of glass transition behavior determined by differential scanning calorimetry, some but not all imidized acrylic structures were found to be miscible with PVC and with SAN copolymers within a limited window of AN levels. Acid functionality in the imidized acrylics appears to hinder their miscibility with SAN rather significantly and with PVC to a lesser extent. Miscible SAN blends showed lower critical solution temperature behavior whereas miscible blends with PVC did not up to the highest attainable temperatures. The composition factors that influence the phase behavior are described and interpreted in terms of possible mechanisms.     

PVC／ABS共混体系的相容性与形态结构研究

采用种子乳液聚合技术在聚丁二烯（PB）乳胶粒子上接枝共聚苯乙烯（St）、α-甲基苯乙烯（α—MSt）和丙烯腈（AN）单体,合成了一系列不同AN结合量的ABS和α—MABS接枝共聚物。将其与聚氯乙烯（PVC）树脂熔融共混制得了PVC／AtkS共混物,利用扫描电镜（SEM）、透射电镜（TEM）和动态力学分析仪（DMA）对共混物的相容性和相结构进行了表征。结果发现,在PVC／ABS共混体系中,尽管改变接枝SAN共聚物的AN结合量,PVC和ABS接枝共聚物均为不相容体系;在ABS接枝共聚物中引入α-MSt后,当接枝SAN共聚物的AN结合量为18．7％～23．6％（质量分数）时,共混物在室温以上只存在1个tanδ峰,共混物成为相容体系,当AN结合量达到32．1％（质量分数）时,共混物成为部分相容体系。共混物的相区尺寸明显地依赖于接枝SAN共聚物中的AN结合量,与动态力学性能结果表现出良好的吻合。     

Phase behavior of binary mixtures of styrene/acrylonitrile copolymers and aliphatic polyesters

The phase behavior of binary mixtures of copolymers containing varying amounts of styrene and acrylonitrile (SAN) with a large range of aliphatic polyesters was examined. Miscibility was observed over a limited range of AN contents of the SANs, for each polyester, while similarly for each SAN, miscibility was only observed over a limited range of polyester molecular structures. Thermodynamic interaction parameters for the miscible blends were obtained by analysis of the depression of the polyester melting point. A binary interaction model was used to correlate the data and six group interaction parameters were deduced by subdividing the polyester and SAN copolymer repeating units in three different ways. It is concluded that there is a strong repulsion between the segmental units within the polyesters and within the SAN copolymers, which is an important factor in the observed phase behavior.     

Miscible and immiscible blends of ABS with PMMA. I. Morphology and rheology

Melt blends of ABS and PMMA were prepared using three types of ABS having different acrylonitrile (AN) content, and PMMAs with different MW. From TEM micrographs, it was found that ABSs containing 24 and 27 wt % AN were miscible, and the one containing 35 wt % AN was immiscible with PMMA. Morphologically miscible blends showed welldefined semicircles in Cole—Cole plots, whereas immiscible ones showed immiscible drifts from the semicircle. In addition, as the compounding temperature increases, the dispersed PMMA phase became stratified, and more rubber particles, especially larger ones, migrated toward the PMMA phase. Miscible blends gave viscosities lower than additivity would predict, whereas immiscible ones gave positive (ABS-rich phase) and negative (PMMA-rich phase) deviations from the additivity. © 1993 John Wiley & Sons, Inc.     

Compatibility behavior in thermoplastic polymer blends containing poly(t-butylstyrene-co-acrylonitrile)

The phase behavior of a series of binary component polymer blends of poly(ε-caprolactone) (PCL) and poly(t-butylstyrene-co-acrylonitrile) (TBSAN) containing varying contents of acrylonitrile (AN) was examined to determine the influence of copolymer composition and PCL content on blend miscibility or immiscibility. Thermal measurements were extensively used to determine phase behavior, i.e., a single compositionally dependent glass transition temperature implies blend miscibility. Otherwise, immiscibility is assumed to dominant blend behavior. It was determined that TBSAN and PCL form miscible blends over a broad range of AN content, i.e., spanning from below 43.2 mol % (19.8 wt %) to about 66.4 mol % (39.6 wt %), a range considerably different from that found in poly(styrene-co-acrylonitrile) copolymers. TBSAN-containing blends were found to be immiscible when the AN content is less than about 43 mol % or greater than about 67 mol %. Small-angle light-scattering and polarized light microscopy was used to probe the substantial morphological changes in the miscible blends. Little change was observed in the immiscible blends. These results clarify the phase separation observed in these blend systems. © 1993 John Wiley & Sons, Inc.     

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.     

Novel blends of alternating propene-carbon monoxide copolymers and styrenic copolymers

Summary Alternating propene-carbon monoxide copolymers (P-CO) were melt-blended with polystyrene, poly(styrene-co-acrylonitrile) (SAN), and with poly(styrene-co-maleic anhydride) (SMA). P-CO forms homogeneously miscible blends with SAN containing 25 wt% AN at the investigated blend compositions. The transparent blends have single, intermediate glass transition temperatures that fit the Fox equation. The elastic properties of P-CO at room temperature disappear upon blending with SAN because the T _g is driven above RT. Polystyrene and SMA are not miscible with P-CO and form heterogeneous blends with two glass transitions. This demonstrates that both the polarity of the styrenic copolymer and the nature of the comonomer govern its phase behavior. Received: 14 January 1999/Revised version: 19 April 1999/Accepted: 19 April 1999     

Compatibility of poly(ϵ-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) blends. II. The influence of the AN content in SAN copolymer upon blend compatibility

The compatibility of polymer blends of poly(?-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) containing various acrylonitrile (AN) contents was studied to evaluate the influences of copolymer composition and PCL concentration upon blend compatibility. Blend compatibility was characterized by the occurence of a single glass transition intermediate between the transitions of the respective pure components. The glass transitions were determined by differential scanning calorimetry (DSC) and dynamic mechanical measurement (Rheovibron). It was found that SAN and PCL form compatible blends when the AN content of SAN ranges from 8% to 28% by weight. These blends are compatible in all proportions except for SAN 28 (AN wt % = 28) and PCL blends containing 70 or 85 wt % PCL. Blends of PCL and SAN were found to be incompatible when the AN content in SAN is greater than 30 wt % or less than 6 wt %. Lower critical solution temperature (LCST) behavior, which can be attributed to phase separation, was found to occur when these blends were heated to elevated temperatures. The cloud point, or phase separation, was found to vary with AN content in SAN and the concentration of SAN in the blend.     

Miscibility and rheological properties of poly(vinyl chloride)/styrene–acrylonitrile blends prepared by melt extrusion

Styrene–acrylonitrile (SAN) with acrylonitrile (AN) concentrations of 11.6–26 wt % and α‐methylstyrene acrylonitrile (αMSAN) with a wide range of AN concentrations are miscible with poly(vinyl chloride) (PVC) through solution blending. Here we examine the rheological properties and miscibility of PVC/SAN and PVC/αMSAN blends prepared by melt extrusion for commercial applications. We have investigated the rheological properties of the blends with a rheometer and a melt indexer. The PVC/SAN and PVC/αMSAN blends have a low melting torque, a long degradation time, and a high melt index, and this means that they have better processability than pure PVC. The miscibility of the blends has been characterized with differential scanning calorimetry, dynamic mechanical thermal analysis, and advanced rheometrics expansion system analysis. The miscibility of the blends has also been characterized with scanning electron microscopy. The SAN series with AN concentrations of 24–31 wt % is immiscible with PVC by melt extrusion, whereas αMSAN with 31 wt % AN is miscible with PVC, even when they are blended by melt extrusion, because of the strong interaction between PVC and αMSAN. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of the composition of α-MSAN copolymer on the miscibility of PVC/α-MSAN blends

A series of α-methylstyrene, styrene, and acrylonitrile (α-MSAN) copolymers with different acrylonitrile (AN) contents were synthesized by altering α-MSt, St, and AN ratios with emulsion copolymerization method. By melt-blending these copolymers with PVC resin and di-isooctyl phthalate (DOP), PVC/α-MSAN, and PVC/α-MSAN/DOP blends were prepared. The miscibility and morphology of the blends were investigated by dynamic mechanical analysis (DMA) and scanning electron microscopy. The PVC is immiscible with SAN by melt-mixing, whereas PVC is miscible with α-MSAN (α-MSt/St = 1/1) if AN weight percent is within the window range of 20–25 wt %, and α-MSAN (not containing St) with 35 wt % AN is miscible with PVC even when they are blended by melt-mixing. Replacement of styrene with α-methylstyrene widens the miscibility window with PVC. The miscibility of PVC/α-MSAN blends is substantially improved with the increasing α-MSt content in α-MSAN copolymer containing identical AN content. When DOP was introduced into the PVC/α-MSAN (α-MSt/St = 1/1) blends, a single tan δ peak over room temperature in DMA detection is found as AN content in α-MSAN copolymer is within the range of 15–25 wt %, and SEM observation also shows that the blends are homogeneous. When the AN content in α-MSAN copolymer is over 35 wt %, the presence of DOP causes the phase domain extended. The phase domain size of the PVC/α-MSAN/DOP blends intensively depends on AN content in α-MSAN copolymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Miscibility and complexation behavior of poly(cyanomethyl methacrylate) and poly(2-cyanoethyl methacrylate) with tertiary amide polymers

The miscibility and complexation behavior of poly(cyanomethyl methacrylate) (PCYMMA) and poly(2-cyanoethyl methacrylate) (PCYEMA) with various tertiary amide polymers was studied. PCYMMA and PCYEMA form interpolymer complexes with poly(N-methyl-N-vinylacetamide) (PMVAc) or poly(N-vinyl-2-pyrrolidone) (PVP) in tetrahydrofuran (THF) solutions. PCYMMA also forms complexes with poly(N,N-dimethylacrylamide) (PDMA) in THF solutions. However, PCYEMA does not form complexes with PDMA in THF solutions, but the THF-cast blends are miscible over the entire composition range. Both PCYMMA and PCYEMA do not form complexes with poly(2-ethyl-2-oxazoline) (PEOx) in THF solutions and are only miscible with PEOx when the blend contains greater than 60 wt % PCYMMA or 80 wt % PCYEMA. On the other hand, both PCYMMA and PCYEMA do not form complexes with PMVAc, PVP, or PDMA in N,N-dimethylformamide (DMF) solutions. The compositions of the complexes consist of simple mole ratios of the component polymers, and the glass-transition temperatures of the complexes are higher than those of the DMF-cast blends of similar compositions. Fourier-transform infrared spectroscopy provides further evidence on the miscibility behavior through changes in the amide carbonyl absorption bands of each tertiary amide polymer in the blends as well as in the cyano absorption band of PCYEMA. © 1995 John Wiley & Sons, Inc.     

Properties of immiscible polymer alloys without compatibilizer

The miscibility and properties of the alloys composed of polyphenylene ether (PPE), polystyrene (PS), and acrylonitrile-styrene (SAN) polymers have been studied. The heat distortion temperature and flexual strength decreased with increasing AN contents in SAN in PPE/SAN alloys because the mutual solubility was poor in the high-AN content region. However, PPE/PS/SAN alloys showed higher heat distortion temperature and higher flexural strength than the PPE/PS miscible alloy and the PPE/SAN immiscible alloy. Furthermore, the PPE/PS/SAN alloy has excellent fluidity. It is a kind of immiscible alloy without a compatibilizer, which shows the excellent properties. The results suggested that there is a so-called “entanglement phase” between two separated phases and PPE distributed to both phases, and this phase is superior to that in which compatibilizer was added to enhance miscibility. Moreover, it is very useful for recycling materials because it does not contain a sophisticated compatibilizer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2515–2520, 1998     

Novel water sorption behavior of emulsion blends

As waterborne emulsions continue to replace their solvent‐based counterparts in various applications, the water resistance of cast films is attracting significant interest. The characterization of the water sorption kinetics and structure–property relationships related to water sorption is, therefore, an important area for investigation. In this study, the water sorption kinetics of emulsion blends were compared with those of their blend components. The investigated blends were at equal weight (dry basis) fractions for each emulsion. The initial water sorption rate for immiscible emulsion blends was found to be significantly higher than composite values of the constituents. This behavior was due to percolation networks in the blends because thermodynamic constraints prevented diffusion across the interface bordering dissimilar particles, leaving a interface enriched with water‐sensitive species. The peak water sorption for the immiscible emulsion blends was lower than the composite values because of the ability of the water‐sensitive species to rapidly diffuse out of the samples due to the percolation network. This behavior existed for room‐temperature‐cast samples and persisted as the time and temperature exposure was increased. Atomic force microscopy results clearly showed the potential for percolation networks in the blends. Higher glass‐transition emulsion polymers [e.g., poly(vinyl acetate)] exhibited similar behavior, and this indicated poor film formation like that for the immiscible emulsion blends. These results indicated that the degree of film formation was critical with respect to the water sorption characteristics of emulsion films. Immiscible emulsion blends were compared with miscible emulsion blends for which all constituents exhibited excellent film formation (unblended). The immiscible blends exhibited a significant difference in water sorption compared with the miscible blends because of the existence of percolation networks. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 933–939, 2003     

Phase behavior of ternary blends containing dimethylpolycarbonate,tetramethylpolycarbonate and poly[styrene‐co‐(methyl methacrylate)] copolymers (or polystyrene)

The miscibility and phase behavior of ternary blends containing dimethylpolycarbonate (DMPC), tetramethylpolycarbonate (TMPC) and poly[styrene‐co‐(methyl methacrylate)] copolymer (SMMA) have been explored. Ternary blends containing polystyrene (PS) instead of SMMA were also examined. Blends of DMPC with SMMA copolymers (or PS) did not form miscible blends regardless of methyl methacrylate (MMA) content in copolymers. However, DMPC blends with SMMA (or PS) blends become miscible by adding TMPC. The miscible region of ternary blends is compared with the previously determined miscibility region of binary blends having the same chemical components and compositions. The region where the ternary blends are miscible is much narrower than that of binary blends. Based on lattice fluid theory, the observed phase behavior of ternary blends was analyzed. Even though the term representing the Gibbs free energy change of mixing for certain ternary blends had a negative value, blends were immiscible. It was revealed that a negative value of the Gibbs free energy change of mixing was not a sufficient condition for miscible ternary blends because of the asymmetry in the binary interactions involved in ternary blends. Copyright © 2004 Society of Chemical Industry     

Miscibility and interpolymer complexation of poly(2-methyl-2-oxazoline) with hydroxyl-containing polymers

Poly(2-methyl-2-oxazoline) (PMOx) was found to be miscible with poly (styrene-coallyl alcohol), poly(hydroxyether of bisphenol-A), poly (2-hydroxypropyl methacrylate) and poly(p-vinylphenol) (PVPh), when cast from N,N-dimethylformamide solutions and to form interpolymer complexes with PVPh in methanol solutions. The hydrogen bonding interactions between PMOx and hydroxyl-containing polymers were studied by infrared spectroscopy and compared with the corresponding blends of poly(2-ethyl-2-oxazoline) (PEOx). Except with phenoxy, PMOx interacts more strongly with hydroxyl-containing polymers than PEOx does.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(styrene-co-acrylonitrile) and poly(p-methylstyrene-co-acrylonitrile)

The miscibility of poly(methoxymethyl methacrylate) (PMOMA) and poly(methylthiomethyl methacrylate) (PMTMA) with poly(styrene-co-acrylonitrile) (SAN) and poly(p-methylstyrene-co-acrylonitrile) (pMSAN) was studied by differential scanning calorimetry. PMOMA is miscible with SAN having an acrylonitrile (AN) content around 30 wt %. However, PMOMA is immiscible with any of the pMSAN having AN contents between 9 and 36 wt % and with pMSAN having AN contents between 19 and 34 wt %. The miscibility of the blends enables the evaluation of various segmental interaction parameters.     

Toughness,dynamic mechanical property,and morphology of polyvinylchloride/acrylonitrile‐styrene‐butyl acrylate blends

Acrylonitrile‐styrene‐butyl acrylate (ASA) graft copolymers with different acrylonitrile (AN) contents, the core‐shell ratio, and tert‐dodecyl mercaptan (TDDM) amounts were synthesized by seed emulsion polymerization. Polyvinylchloride (PVC)/ASA blends were prepared by melt blending ASA graft copolymers with PVC resin. Then the toughness, dynamic mechanical property, and morphology of the PVC/ASA blends were investigated. The results indicated that the impact strength of the PVC/ASA blends increased and then decreased with the increase of the AN content in poly(styrene‐co‐acrylonitrile (SAN) copolymer, and increased with the increase of the core‐shell ratio of ASA. It was shown that brittle‐ductile transition of PVC/ASA blends was dependent on poly(butyl acrylate) (PBA) rubber content in blends and independent of AN content in SAN copolymer. The introduction of TDDM made the toughness of PVC/ASA blends poor. Dynamic mechanical analysis (DMA) curves exhibited that PVC and SAN copolymers were immiscible over the entire AN composition range. From scanning electron microscopy (SEM), it was found that the dispersion of ASA in PVC/ASA blends was dependent on the AN content in SAN copolymer and TDDM amounts. J. VINYL ADDIT. TECHNOL., 22:43–50, 2016. © 2014 Society of Plastics Engineers