The effects of PC‐PMMA block copolymer on the compatibility and interfacial properties of PC/SAN blends

Block copolymers of polycarbonate (PC) and polymethylmethacrylate (PMMA), PCb‐PMMA, were examined as compatibilizers for blends of PC with styrene‐co‐acrylonitrile (SAN) copolymer. PC‐b‐PMMA was added to blends of PC with SAN containing various amounts of AN. The average diameter of the dispersed particles was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fiber retraction (IFR) test and an asymmetric double cantilever beam fracture test. The average particle size and interfacial tension of the PC/SAN blends reached a minimum value when the SAN copolymer contained about 24 wt% AN. A maximum in the adhesion energy was also observed at the same AN content. Interfacial tension and particle size were further reduced by adding PC‐b‐PMMA to the PC/SAN blends. Fracture toughness of the blends was also improved by enhancing the interfacial adhesion by the addition of PC‐b‐PMMA. The addition of PC‐b‐PMMA copolymer was more effective at improving the interfacial properties of PC/SAN blends than was varying the AN content of the SAN copolymers. The interfacial properties of the PC/SAN blends were optimized by adding a block copolymer and using an SAN copolymer that had minimum interaction energy with PC.     

Effects of tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) copolymers containing various amounts of acrylonitrile on the interfacial properties of polycarbonate and poly(styrene‐co‐acrylonitrile) blends

Tetramethylpolycarbonate‐block‐poly(styrene‐co‐acrylonitrile) (TMPC‐block‐SAN) block copolymers containing various amounts of acrylonitrile (AN) were examined as compatibilizers for blends of polycarbonate (PC) with poly(styrene‐co‐acrylonitrile) (SAN) copolymers. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fibre retraction technique and an asymmetric double‐cantilever beam fracture test. Reduction in the average diameter of dispersed particles and effective improvement in the interfacial properties was observed by adding TMPC‐block‐SAN copolymers as compatibilizer of PC/SAN blend. TMPC‐block‐SAN copolymer was effective as a compatibilizer when the difference in the AN content of SAN copolymer and that of SAN block in TMPC‐block‐SAN copolymer was less than about 10 wt%. Copyright © 2004 Society of Chemical Industry     

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     

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 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.     

Changes in the interfacial properties of PC/SAN blends with compatibilizer

Block copolymers of polycarbonate‐b‐poly(methyl methacrylate) (PC‐b‐PMMA) and tetramethyl poly(carbonate)‐b‐poly(methyl methacrylate) (TMPC‐b‐PMMA) were examined as compatibilizers for blends of polycarbonate (PC) with styrene‐co‐acrylonitrile (SAN) copolymer. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fiber retraction (IFR) technique and an asymmetric double cantilever beam fracture test. The average diameter of dispersed particles and interfacial tension of the PC/SAN blends were reduced by adding compatibilizer to the PC/SAN blends. Fracture toughness of the blends was also improved by enhancing interfacial adhesion with compatibilizer. TMPC‐b‐PMMA copolymer was more effective than PC‐b‐PMMA copolymer as a compatibilizer for the PC/SAN blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2649–2656, 2003     

Miscibility of polyethyloxazoline with thermoplastic polymers

Polyethyloxazoline (PEOx) blends with several other thermoplastic polymers were examined by differential scanning calorimetry (DSC) for miscibility. Styrene/acrylonitrile (SAN) copolymers having compositions in the range of about 20–40% acrylonitrile (AN) by weight were found to be miscible with PEOx whereas SANs outside this range were not. The polyhydroxyl ether of bisphenol A (Phenoxy) was also found to be miscible with PEOx. A vinylidene chloride copolymer (Saran) was found to be partially miscible with PEOx, whereas poly(methyl methacrylate) and polycarbonate were not miscible at all.     

Effect of intramolecular interactions on the miscibility windows of PVC blends with modified SAN copolymers

We investigated the miscibility windows in the blends of poly(vinyl chloride) (PVC) with chemically modified styrene/acrylonitrile (SAN) copolymers such as α-methyl styrene/acrylonitrile (α SAN), α-methyl styrene/methacrylonitrile (MSMAN). The blends of PVC with α SAN were found to have the broader miscibility window. This enhanced miscibility was interpreted in terms of intramolecular repulsion that originates from unfavorable interaction between counits of the copolymers and also intramolecular association of AN units. The intramolecular interactions were studied by using Fourier transform infrared (FT-IR) spectroscopy. These interactions were reflected by a peak broadening in the nitrile stretching band in the acrylonitrile segments. The intermolecular interactions governing the miscibility in the blends of PVC with the series of copolymers were also discussed.     

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。     

Interfacial shear strength and wettability between glass fiber and PC/SAN/SMA blends

The two important factors affecting the mechanical properties of fiber‐reinforced composite materials are the interfacial shear strength (IFSS) and wettability. The IFSS and wettability of glass fiber in a polycarbonate (PC)/styrene‐co‐acrylonitrile (SAN) blend system were measured by the single fiber fragmentation test (SFFT) and the Wilhelmy method, respectively. Styrene‐co‐maleic‐anhydride (SMA) was used as a compatibilizer and the glass fiber was surface‐treated with organosilane coupling agents to induce chemical bonding between maleic anhydride and silanol. The IFSS was found to increase with the content of SMA copolymer and then level off: There was an optimum level of the SMA content for a given silanol content. The IFSS and wettability increased with increasing SAN content, and the wettability showed quite similar behavior to the case of the IFSS with respect to SAN content. The effect of the miscibility of SAN/SMA blends on the IFSS was also investigated. The IFSS was greatly affected by the miscibility of SAN/SMA blends, which is mainly dependent on the copolymer compositions of SAN and SMA. Higher IFSS was obtained when the SAN/SMA blend was miscible.     

Effects of AN-contents and shear flow on the miscibility of PC/SAN blends

The miscibility of polycarbonate (PC) with styrene-co-acrylonitrile random copolymer (SAN) has been systematically investigated as functions of acrylonitrile content and shear flow. Various AN-contents ranged from 11 to 74 wt% and different simple shear flow values up to 90 s⁻¹ have been used to explore the effect of both material and proceeding parameters on the miscibility of PC and SAN blends. The finest phase dispersion of the SAN particles was observed at AN=25 wt% for PC/SAN=70/30 blends under the same processing condition using scanning electron microscope (SEM). The obtained morphologies indicated that PC and SAN could form a partial miscibility blend and the maximum miscibility occurred at AN=25 wt%. This observation was supported by considering the shifts in the glass processes of the two rich phases of the blend using the dynamical mechanical analysis (DMA) measurements. The optimum interaction of the two components at AN=25 wt% calculated from ellipsometric technique was found to be the only responsible parameter for the high miscibility of the blend. The viscoelastic properties of the pure polymer components were found to play a minor role in the obtained morphologies. The effect of simple shear flow on the morphology of PC/SAN-25=70/30 blend has been also investigated using a special shear apparatus of parallel plate geometry. It has been found that the dispersed phase of SAN was elongated and broken-up in the direction of flow with weaker contrast at high shear rates. The shear rate was found to enhance the miscibility of SAN (dispersed phase) in the PC matrix to a great extent as seen in the weak contrast of the two phases observed by transmission electron microscope (TEM).     

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     

Influence of blend composition on the mechanical properties and morphology of PC/ASA/SAN ternary blends

Bisphenol A polycarbonate/acrylonitrile–styrene–acrylic/styrene–acrylonitrile copolymer (PC/ASA/SAN) ternary blends were prepared over a range of compositions via mixing PC, SAN, and ASA copolymer by melt blending. An analysis was made on the mechanical properties and morphology of the blends. Special care was taken to make comparisons of the morphologies and properties of blends with different SAN content. When a small amount SAN was introduced to PC/ASA blends, the dispersion condition of ASA in the matrix was improved and a better integrated mechanical properties was realized. Further increasing the SAN content led to a decrease of impact strength, which was due to the changing of the morphology of the blends and the inherent brittleness of matrix. The study about the effect of ASA content on the properties of PC/ASA/SAN blends showed that the blend with 20 wt% ASA had good mechanical properties.     

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.     

Morphology and physical properties of SAN/NBR blends: The effect of AN content in NBR

Poly(styrene‐co‐acrylonitrile) (SAN), of which the content of acrylonitrile (AN) repeating unit is 32 wt % (SAN32), was blended with poly(butadiene‐co‐acrylonitrile) (NBR). The effects of AN repeating unit content in NBR on the miscibility, morphology, and physical properties of SAN32/NBR (70/30 by weight) blends were studied. Differential scanning calorimetry and the morphology observed by transmission electron microscopy showed that the miscibility between SAN32 and NBR was increased as the AN content in NBR was increased up to 50 wt %. The impact strength and some other mechanical properties of the blends had the maximum value when the AN content in NBR was 34 wt %. In the measurement of viscoelasticity at melt state, SAN32/NBR blends showed yield behavior at low shear rate, and this behavior was most evident when the AN content in NBR was 34 wt %. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1861–1868, 2000     

Phase morphology characterization and ultimate mechanical properties of 60/40 PC/SAN blend: Influence of the acrylonitrile content of SAN

The tensile stress-strain properties of blends having a 60/40 weight ratio of polycarbonate of bisphenol-A (PC) and styrene-acrylonitrile copolymers (SAN) have been investigated for a range of SAN copolymers with different AN levels. It is clearly demonstrated that the phase morphology of these, blends and the acrylonitrile (AN) content of the SAN component are important factors with respect to the ultimate mechanical properties (tensile strength and elongation at fracture). Following injection molding, a very fine phase distribution is observed for blends with SAN components containing 15 to 29% AN. By annealing of the blends at 200°C, i.e. above T_g(PC), it has been possible to obtain different degrees of domain sizes. From this range of morphologies, quite similar phase structures can selected differing only in AN-content of the SAN blend components. This allows a systematic investigation of the effect of the AN-content on the tensile stress-strain. Properties of PC/SAN blends. The elongation at fracture exhibits an optimum for blends with SAN containing 24% AN. A coarsening of the phase morphology only results in a decrease of the ductility and not in a shift of the optimum. The maximum tensile stress exhibits a sigmoidal trend as a function of the AN-content. This parameter remains constant for a typical -PC/SAN blend with different morphologies.     

Miscibility windows in ternary polymer blends of a polyester,polymethacrylate and poly(styrene‐co‐acrylonitrile)

Miscibility, phase diagrams and morphology of poly(ε‐caprolactone) (PCL)/poly(benzyl methacrylate) (PBzMA)/poly(styrene‐co‐acrylonitrile) (SAN) ternary blends were investigated by differential scanning calorimetry (DSC), optical microscopy (OM), and scanning electron microscopy (SEM). The miscibility window of PCL/PBzMA/SAN ternary blends is influenced by the acrylonitrile (AN) content in the SAN copolymers. At ambient temperature, the ternary polymer blend is completely miscible within a closed‐loop miscibility window. DSC showed only one glass transition temperature (T_g) for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends; furthermore, OM and SEM results showed that PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 were homogeneous for any composition of the ternary phase diagram. Hence, it demonstrated that miscibility exists for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends, but that the ternary system becomes phase‐separated outside these AN contents. Copyright © 2003 Society of Chemical Industry     

Enthalpic effects on interfacial adhesion of immiscible polymers compatibilized with block copolymers

The influence of enthalpic interactions on interfacial adhesion between immiscible polymer matrices and reinforcing block copolymer segments has been studied using the transmission electron microscopic (TEM) methodology of Creton et al. We examined the behaviour of four statistical styrene-acrylonitrile (SAN) copolymers, each having different acrylonitrile (AN) content, blended with polystyrene (PS) as the minor component, and reinforced by three poly(methyl methacrylate-b-styrene) (PMMA-b-PS) block copolymers of differing molar masses, viz. 20000, 65000 and 680000 g mol⁻¹. These observations were compared with similar experiments on poly(methyl methacrylate) (PMMA) blended with PS and reinforced by PMMA-b-PS. Emulsification was observed with all three PMMA-b-PS copolymers. Crazes were formed in the SAN matrices and a statistical evaluation of interfacial failures was performed on the discrete PS domains that lay within the crazes. For the two block copolymers of higher molar mass, optimal reinforcement of the interfaces was observed independent of the SAN composition. With the 20000 block copolymer, however, the pattern of the interfacial failure depended strongly on the SAN composition. Specifically, it was observed that the fraction of the discrete particles that suffered interfacial failure, and led to the creation of large voids in the crazes in these blends, increased with increased AN content of the SAN matrix. Thus, we found that the fraction of discrete PS particles that produce large voids in crazes of blends containing SAN33 is always higher than in blends containing SAN15, when reinforced with the 20000 PMMA-b-PS. We infer that the critical molar mass required of a mechanically reinforcing copolymer depends on the short-range (attractive and repulsive) interactions between the blend components in the interfacial region. The TEM method could not, however, distinguish between reinforced and neat PMMA/PS blends, all of which showed strong adhesion. This is attributed to the comparatively diffuse interface in the PMMA/PS system, a consequence of the relatively weak repulsion between these two polymers.     

Effect of copolymer composition on the miscibility of blends of styrene-acrylonitrile copolymers with poly (methyl methacrylate)

The phase behaviour for blends of various polymethacrylates with styrene-acrylonitrile (SAN) copolymers has been examined as a function of the acrylonitrile content of the copolymer. Poly(methyl methacrylate), poly(ethyl methacrylate) and poly(n-propyl methacrylate) were found to be miscible with SANs over a limited window of acrylonitrile contents while no SANs appear to be miscible with poly(isopropyl methacrylate) or poly(n-butyl methacrylate). These conclusions were reached on the basis of lower critical solution temperature (LCST) and glass transition temperature behaviour. All miscible blends exhibited phase separation on heating, LCST behaviour, at temperatures which varied greatly with copolymer composition. An optimum acrylonitrile (AN) level ranging from about 10 to 14% by weight resulted in the highest temperatures for phase separation which has important implications for selection of SANs to produce homogeneous mixtures by melt processing. The basis for miscibility in these systems is evidently repulsion between styrene and acrylonitrile units in the copolymer as explained by recent models. The excess volumes for all blends are zero within experimental accuracy which suggests that the interactions for miscibility are relatively weak even for the optimum AN level. This interaction becomes smaller the larger or more bulky is the alkyl side group of the polymethacrylate.     

Miscibility of poly(styrene-co-acrylonitrile) with random copolymers of tetramethyl bisphenol-A polyarylate and tetrabromo bisphenol-A polyarylate

Summary Tetramethyl bisphenol-A polyarylate (TMPAR) was miscible with poly(styrene-coacryloni trile) 's(SANs) containing 4, 7, 10, and 13wt% of acrylonitrile(AN) repeating unit. As the content of tetrabromo bisphenol-A polyarylate(TBPAR) repeating unit in the random copolymer of TMPAR and TBPAR was increased, the miscibility window in the blends with SANs was narrowed. The intramolecular repulsion between styrene and AN repeating units in SAN was suggested to be the main driving force for the miscibility of SANs with the random copolymers of TMPAR and TBPAR.