Effect of in situ polymerization conditions of methyl methacrylate on the structural and morphological properties of poly(methyl methacrylate)/poly(acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene)‐g‐styrene) PMMA/AES Blends

In this study, the structural and morphological properties of poly(methyl methacrylate)/poly(acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene‐g‐styrene) (PMMA‐AES) blends were investigated with emphasis on the influence of the in situ polymerization conditions of methyl methacrylate. PMMA‐AES blends were obtained by in situ polymerization, varying the solvent (chloroform or toluene) and polymerization conditions: method A—no stirring and air atmosphere; method B—stirring and N₂ atmosphere. The blends were characterized by infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA). The results showed that the PMMA‐AES blends are immiscible and present complex morphologies. This morphology shows an elastomeric dispersed phase in a glassy matrix, with inclusion of the matrix in the elastomer domains, suggesting core shell or salami morphology. The occlusion of the glassy phase within the elastomeric domains can be due to the formation of graft copolymer and/or phase inversion during polymerization. However, this morphology is affected by the polymerization conditions (stirring and air or N₂ atmosphere) and by the solvent used. The selective extraction of the blends' components and infrared spectroscopy showed that crosslinked and/or grafting reactions occur on the elastomer chains during MMA polymerization. The glass transition of the elastomer phase is influenced by morphology, crosslinking, and grafting degree and, therefore, T_g depends on the polymerization conditions. On the other hand, the behavior of T_g of the glassy phase with blend composition suggests miscibility or partial miscibility for the SAN phase of AES and PMMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dynamic mechanical and morphological behavior of blends of polystyrene and poly[acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene)‐g‐styrene] prepared by in situ polymerization of styrene

PS/AES blends were prepared by in situ polymerization of styrene in the presence of AES elastomer, a grafting copolymer of poly(styrene‐co‐acrylonitrile) – SAN and poly(ethylene‐co‐propylene‐co‐diene)–EPDM chains. These blends are immiscible and present complex phase behavior. Selective extraction of the blends' components showed that some fraction of the material is crosslinked and a grafting of PS onto AES is possible. The morphology of the noninjected blends consists of spherical PS domains covered by a thin layer of AES. After injection molding, the blends show morphology of disperse elastomeric phase morphology in a rigid matrix. Two factors could contribute to the change of morphology: (1) the stationary polymerization conditions did not allow the mixture to reach the equilibrium morphology; (2) the grafting degree between PS and AES was not high enough to ensure the morphological stability against changes during processing in the melting state. The drastic change of EPDM morphology from continuous to disperse phase has as consequence a decrease in the intensity of the loss modulus peaks corresponding to the EPDM glass transition. However, the storage modulus at temperatures between the glass transition of EPDM and PS/SAN phases does not change significantly. This effect was attributed to the presence of the SAN rigid chains in the AES. © 2009 Wiley Periodicals, Inc. Journal of Applied Polymer Science, 2009     

Effects of compatibilizer on the morphological,mechanical, and rheological properties of poly(methyl methacrylate)/poly(N‐methyl methacrylimide) blends

The effects of compatibilizer on the morphological, thermal, mechanical, and rheological properties of poly(methyl methacrylate) (PMMA)/poly(N‐methyl methacrylimide) (PMMI) (70/30) blends were investigated. The compatibilizer used in this study was styrene–acrylonitrile–glycidyl methacrylate (SAN‐GMA) copolymer. Morphological characterization of the PMMA/PMMI (70/30) blend with SAN‐GMA showed a decrease in PMMI droplet size with an increase in SAN‐GMA. The glass‐transition temperature of the PMMA‐rich phase became higher when SAN‐GMA was added up to 5 parts per hundred resin by weight (phr). The flexural and tensile strengths of the PMMA/PMMI (70/30) blend increased with the addition of SAN‐GMA up to 5 phr. The complex viscosity of the PMMA/PMMI (70/30) blends increased when SAN‐GMA was added up to 5 phr, which implies an increase in compatibility between the PMMA and PMMI components. From the weighted relaxation spectrum, which was obtained from the storage modulus and loss modulus, the interfacial tension of the PMMA/PMMI (70/30) blend was calculated using the Palierne emulsion model and the Choi‐Schowalter model. The results of the morphological, thermal, mechanical, and rheological studies and the values of the interfacial tension of the PMMA/PMMI (70/30) blends suggest that the optimum compatibilizer concentration of SAN‐GMA is 5 phr. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43856.     

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     

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     

Effects of the polybutadiene/poly(styrene‐co‐acrylonitrile) ratio in a polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) impact modifier on the morphology and mechanical behavior of acrylonitrile–butadiene–styrene blends

Polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) (PB‐g‐SAN) impact modifiers with different polybutadiene (PB)/poly(styrene‐co‐acrylonitrile) (SAN) ratios ranging from 20.5/79.5 to 82.7/17.3 were synthesized by seeded emulsion polymerization. Acrylonitrile–butadiene–styrene (ABS) blends with a constant rubber concentration of 15 wt % were prepared by the blending of these PB‐g‐SAN copolymers and SAN resin. The influence of the PB/SAN ratio in the PB‐g‐SAN impact modifier on the mechanical behavior and phase morphology of ABS blends was investigated. The mechanical tests showed that the impact strength and yield strength of the ABS blends had their maximum values as the PB/SAN ratio in the PB‐g‐SAN copolymer increased. A dynamic mechanical analysis of the ABS blends showed that the glass‐transition temperature of the rubbery phase shifted to a lower temperature, the maximum loss peak height of the rubbery phase increased and then decreased, and the storage modulus of the ABS blends increased with an increase in the PB/SAN ratio in the PB‐g‐SAN impact modifier. The morphological results of the ABS blends showed that the dispersion of rubber particle in the matrix and its internal structure were influenced by the PB/SAN ratio in the PB‐g‐SAN impact modifiers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2165–2171, 2005     

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.     

Enhancing electrical properties of MWCNTs in immiscible blends of poly(methyl methacrylate) and styrene‐acrylonitrile copolymer by selective localization

Multiwalled carbon nanotubes (MWCNTs) were introduced into poly(methyl methacrylate) (PMMA) and styrene‐acrylonitrile copolymer (SAN) blends by melt mixing in an asymmetric miniature mixer (APAM). A composition of 70 wt% of PMMA and 30 wt% of SAN was mixed to create a co‐continuous morphology. Transmission electron microscopy images of ultra‐microtomed samples (70 nm in thickness) showed selective localization of MWCNTs inside the percolated SAN phase. The occurrence of the double percolation phenomenon resulted in lower electrical percolation thresholds of PMMA/SAN/MWCNT blends molded at high temperatures. Dielectric spectroscopy indicated a higher electrical permittivity for samples that were compression molded at 260°C. Due to the higher affinity of MWCNTs to SAN, there was a migration of MWCNTs into the SAN phase during the melt processing. Conductivity measurements revealed a significant decrease in electrical percolation threshold (0.4 wt%) for PMMA70/SAN30 blends compared with MWCNT‐filled SAN and MWCNT‐filled PMMA (ca. 0.8 wt%). POLYM. COMPOS., 37:1523–1530, 2016. © 2014 Society of Plastics Engineers     

Polycarbonate/acrylonitrile–styrene–acrylic elastomer terpolymer blends with enhanced interfacial adhesion and surface gloss

A blend of bisphenol A polycarbonate (PC) and an acrylonitrile–styrene–acrylic elastomer (ASA) terpolymer with high surface gloss and excellent interfacial properties was developed for automobile applications. Because PC and the styrene‐co‐acrylonitrile (SAN) copolymer that formed the matrix in the PC/ASA blend were not miscible, two different types of compatibilizers were examined to improve the compatibility of the blend. A diblock copolymer composed of tetramethyl polycarbonate and poly(methyl methacrylate) (PMMA) was more effective than PMMA in increasing interfacial adhesion between PC and SAN. The surface gloss of the PC/ASA blend was always lower than that of the pure ASA included in the blend because of PC existing at the surface of the injection‐molding specimen. The PC/ASA blend with optimum surface gloss and enhanced interfacial adhesion was developed through the control of the molecular weight of PC and the compatibilizer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2097–2104, 2005     

Effects of addition of acrylic compatibilizer on the morphology and mechanical behavior of amorphous polyamide/SAN blends

Amorphous polyamide (aPA)/acrylonitrile‐styrene copolymer (SAN) blends were prepared using methyl methacrylate‐maleic anhydride copolymer MMA‐MA as compatibilizer. The aPA/SAN blends can be considered as a less complex version of the aPA/ABS (acrylonitrilebutadiene‐styrene) blends, due to the absence of the ABS rubber phase in the SAN material. It is known that acrylic copolymer might be miscible with SAN, whereas the maleic anhydride groups from MMA‐MA can react in situ with the amine end groups of aPA during melt blending. As a result, it is possible the in situ formation of aPA‐g‐MMA‐MA grafted copolymers at the aPA/SAN interface during the melt processing of the blends. In this study, the MA content in the MMA‐MA copolymer and its molecular weight was varied independently and their effects on the blend morphology and stress–strain behavior were evaluated. The morphology of the blends aPA/SAN showed a minimum in the SAN particle size at low amounts of MA in the compatibilizer, however, as the MA content in the MMA‐MA copolymer was increased larger SAN particle sizes were observed in the systems. In addition, higher MA content in the compatibilizer lead to less ductile aPA/SAN blends under tensile testing. The results shown the viscosity ratio also plays a very important role in the morphology formation and consequently on the properties of the aPA/SAN blends studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of acrylonitrile–butadiene–styrene (ABS) morphology and poly(styrene‐co‐acrylonitrile) (SAN) content on fracture behavior of ABS/SAN blends

This study attempted to correlate morphological changes and physical properties for a high rubber content acrylonitrile–butadiene–styrene (ABS) and its diluted blends with a poly(styrene‐co‐acrylonitrile) (SAN) copolymer. The results showed a close relationship between rubber content and fracture toughness for the blends. The change of morphology in ABS/SAN blends explains in part some deviations in fracture behavior observed in ductile–brittle transition temperature shifts. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2606–2611, 2004     

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.     

Phase morphology and thermomechanical analysis of poly(styrene‐co‐acrylonitrile)/ethylene–propylene–diene monomer blends: Uncompatibilized and reactively compatibilized blends with two mixing sequences

The phase morphology developing in immiscible poly(styrene‐co‐acrylonitrile) (SAN)/ethylene–propylene–diene monomer (EPDM) blends was studied with an in situ reactively generated SAN‐g‐EPDM compatibilizer through the introduction of a suitably chosen polymer additive (maleic anhydride) and 2,5‐dimethyl‐2,5‐di‐(t‐butyl peroxy) hexane (Luperox) and dicumyl peroxide as initiators during melt blending. Special attention was paid to the experimental conditions required for changing the droplet morphology for the dispersed phase. Two different mixing sequences (simple and two‐step) were used. The product of two‐step blending was a major phase surrounded by rubber particles; these rubber particles contained the occluded matrix phase. Depending on the mixing sequence, this particular phase morphology could be forced or could occur spontaneously. The composition was stabilized by the formation of the SAN‐g‐EPDM copolymer between the elastomer and addition polymer, which was characterized with Fourier transform infrared. As for the two initiators, the blends with Luperox showed better mechanical properties. Scanning electron microscopy studies revealed good compatibility for the SAN/EPDM blends produced by two‐step blending with this initiator. Dynamic mechanical thermal analysis studies showed that the two‐step‐prepared blend with Luperox had the best compatibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology and electrical properties of polymethylmethacrylate/poly(styrene‐co‐acrylonitrile)/multi‐walled carbon nanotube nanocomposites

Nanocomposites of blends of polymethylmethacrylate (PMMA) and poly(styrene‐co‐acrylonitrile) (SAN) with multi‐walled carbon nanotubes (MWCNTs) were prepared by melt mixing in a twin‐screw extruder. The dispersion state of MWCNTs in the matrix polymers was investigated using transmission electron microscopy. Interestingly enough, in most of the nanocomposites, the MWCNTs were observed to be mainly located at SAN domains, regardless of the SAN compositions in the PMMA/SAN blend and of the processing method. One possible reason for this morphology may be the π–π interactions between MWCNTs and the phenyl ring of SAN. The shift in G‐band peak observed in the Raman spectroscopy may be the indirect evidence proving these interactions. The percolation threshold for electrical conductivity of PMMA/SAN/MWCNT nanocomposites was observed to be around 1.5 wt %. Nanocomposites with PMMA‐rich composition showed higher electrical conductivity than SAN‐rich nanocomposites at a fixed MWCNT loading. The dielectric constant measurement also showed composition‐dependent behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The study of morphology,thermal and thermo‐mechanical properties of compatibilized TPU/SAN blends

The compatibilizing efficiency of three different compatibilizers in thermoplastic polyurethane/styrene‐co‐acrylonitrile (TPU/SAN) blends was investigated after their incorporation via melt‐mixing. The compatibilizers studied were poly‐ε‐caprolactone (PCL), a mixture of polystyrene‐block‐polycaprolactone (PS‐b‐PCL) and polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA), and a mixture of polyisoprene‐block‐polycaprolactone (PI‐b‐PCL) and polybutadiene‐block‐poly(methyl methacrylate) (PB‐b‐PMMA). All compatibilizers were synthesized by living anionic polymerization. Investigations of thermal and thermo‐mechanical properties performed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DTMA), respectively, were systematically classified into two groups, i.e. blends of TPU or SAN with 20 wt% of different compatibilizers (so‐called limit conditions) and TPU/SAN 25/75 blends with 5 wt% of different compatibilizers. In order to determine the compatibilizer's location, morphology of TPU/SAN 25/75 blends was studied with transmission electron microscopy (TEM). Different compatibilization activity was found for different systems. Blends compatibilized with PCL showed superior properties over the other blends. Polym. Eng. Sci. 44:838–852, 2004. © 2004 Society of Plastics Engineers.     

Effect of matrix SAN in ABS/PMMA blends

The effect of the molecular weight and acrylonitrile (AN) content of the styrene–acrylonitrile copolymer (SAN) on the morphology, mechanical properties, and rheological properties of acrylonitrile–butadiene–styrene terpolymer/poly(methyl methacrylate) (ABS)/PMMA (60/40 by weight) blends were studied. When the AN content of matrix SAN (32%) was close to that of graft SAN (30%) AN, rubber particles existed separately. However, with matrix SAN having 35% AN, rubber particles showed tendency to agglomerate each other. With increasing molecular weight of matrix SAN, impact strength, ultimate elongation, and abrasion resistance of the blend generally increased. Yield strength increased with molecular weight at a constant AN content of matrix SAN, and it decreased with the decrease of AN content in spite of the increasing molecular weight of SAN. Melt properties, rather than the morphological and mechanical properties, were more sensitive to the AN content, rather than the molecular weight of matrix SAN. © 1994 John Wiley & Sons, Inc.     

Weld‐line characteristics of polycarbonate/acrylonitrile–butadiene–styrene blends. I. Effect of the processing temperature

The effects of the processing temperature on the morphology and mechanical properties at the weld line of 60/40 (w/w) polycarbonate (PC)/acrylonitrile–butadiene–styrene (ABS) copolymer blends were investigated. The influences of the incorporation of poly(methyl methacrylate) (PMMA) as a compatibilizer and an increase in the viscosity of the dispersed ABS domain phase were also studied. The ABS domain was well dispersed in the region below the V notch, and a coarse morphology in the core region was observed. When tensile stress was applied perpendicularly to the weld line, the fracture propagated along the weak region behind the weld part; there, the domain phase coalescence was significant because of the poor compatibility between PC and styrene–acrylonitrile (SAN). Phase coalescence became severe, and so the mechanical strength of the welded specimen decreased with an increasing injection‐molding temperature. The domain morphology became stable and the mechanical strength increased as the viscosity of the domain phase increased or some SAN was replaced with PMMA. That the morphology was well distributed behind the weld line and the mechanical properties of PC/ABS/PMMA blends were improved was attributed to the compatibilizing effect of PMMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 689–699, 2005     

Micromechanical processes and failure phenomena in reactively compatibilized blends of polyamide 6 and styrenic polymers. II. Polyamide 6/styrene‐acrylonitrile copolymer blends

This work reports on morphological, mechanical, and micromechanical properties of polyamide 6 (PA 6), a styrene‐acrylonitrile copolymer (SAN), and their blends, which were reactively compatibilized using a styrene‐acrylonitrile maleic anhydride (SANMA) terpolymer. Transmission electron microscopy (TEM) investigations revealed the phase morphology of the blends, which is characterized by inclusions of the minor component in the matrix of the major phase. The blend with 50% PA 6 and 50% SAN depicted a cocontinuous morphology. Using a microtensile device for TEM, the samples were deformed under uniaxial loading in the “dry” state (characterized by a zero water content in the PA 6 phase) and in a “wet” state (with water in the PA 6 phase). Whereas the dry blends behaved brittle, the wet blends showed a larger ductility with the formation of deformation bands in the matrix (PA 6 or SAN), which were initiated by stress concentration at the SAN and PA 6 particles, respectively. In the interface of blends with a PA 6 matrix and SAN inclusions, two phenomena were observed: partial cavitation and debonding on the one hand and partial fibrillation on the other hand. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Nanostructured polymer blends based on polystyrene‐b‐polybutadiene‐b‐poly(methyl methacrylate) triblock copolymers modified with polystyrene and/or poly(methyl methacrylate) homopolymers

Morphologies of polymer blends based on polystyrene‐b‐ polybutadiene‐b ‐poly(methyl methacrylate) (SBM) triblock copolymer were predicted, adopting the phase diagram proposed by Stadler and co‐workers for neat SBM block copolymer, and were experimentally proved using atomic force microscopy. All investigated polymer blends based on SBM triblock copolymer modified with polystyrene (PS) and/or poly(methyl methacrylate) (PMMA) homopolymers showed the expected nanostructures. For polymer blends of symmetric SBM‐1 triblock copolymer with PS homopolymer, the cylinders in cylinders core?shell morphology and the perforated lamellae morphology were obtained. Moreover, modifying the same SBM‐1 triblock copolymer with both PS and PMMA homopolymers the cylinders at cylinders morphology was reached. The predictions for morphologies of blends based on asymmetric SBM‐2 triblock copolymer were also confirmed experimentally, visualizing a spheres over spheres structure. This work presents an easy way of using PS and/or PMMA homopolymers for preparing nanostructured polymer blends based on SBM triblock copolymers with desired morphologies, similar to those of neat SBM block copolymers. © 2017 Society of Chemical Industry     

Nanophase morphology and crystallization in poly(vinylidene fluoride)/polydimethylsiloxane‐block‐poly(methyl methacrylate) blends

A polydimethylsiloxane‐block‐poly(methyl methacrylate) (PDMS‐b‐PMMA) diblock copolymer was synthesized by the atom transfer radical polymerization method and blended with a high‐molecular‐weight poly(vinylidene fluoride) (PVDF). In this A‐b‐B/C type of diblock copolymer/homopolymer system, semi‐crystallizable PVDF (C) and PMMA (B) block are miscible due to favorable intermolecular interactions. However, the A block (PDMS) is immiscible with PVDF and therefore generates nanostructured morphology via self‐assembly. Crystallization study reveals that both α and γ crystalline phases of PVDF are present in the blends with up to 30 wt% of PDMS‐b‐PMMA block copolymer. Adding 10 wt% of PVDF to PDMS‐b‐PMMA diblock copolymer leads to worm‐like micelle morphology of PDMS of 10 nm in diameter and tens of nanometers in length. Moreover, morphological results show that PDMS nanostructures are localized in the inter‐fibrillar region of PVDF with the addition of up to 20 wt% of the block copolymer. Increase of PVDF long period by 45% and decrease of degree of crystallization by 34% confirm the localization of PDMS in the PVDF inter‐fibrillar region. © 2018 Society of Chemical Industry