Amphiphilic block copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene: synthesis and self‐assembly

The triblock energetic copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene (PLA‐b‐GAP‐b‐PS) was synthesized successfully through atom‐transfer radical polymerization (ATRP) of styrene and ring‐opening polymerization of d,l ‐lactide. The energetic macroinitiator GAP‐Br, which was made from reacting equimolar GAP with α‐bromoisobutyryl bromide, firstly triggered the ATRP of styrene with its bromide group, and then the hydroxyl group on the GAP end of the resulting diblock copolymer participated in the polymerization of lactide in the presence of stannous octoate. The triblock copolymer PLA‐b‐GAP‐b‐PS had a narrow distribution of molecular weight. In the copolymer, the PS block was solvophilic in toluene and improved the stability of the structure, the PLA block was solvophobic in toluene and served as the sacrificial component for the preparation of porous materials, and GAP was the basic and energetic material. The three blocks of the copolymer were fundamentally thermodynamically immiscible, which led to the self‐assembly of the block copolymer in solution. Further studies showed that the concentration and solubility of the copolymer and the polarity of the solvent affected the morphology and size of the micelles generated from the self‐assembly of PLA‐b‐GAP‐b‐PS. The micelles generated in organic solvents at 10 mg mL^?1 copolymer concentration were spherical but became irregular when water was used as a co‐solvent. The spherical micelles self‐assembled in toluene had three distinct layers, with the diameter of the micelles increasing from 60 to 250 nm as the concentration of the copolymer increased from 5 to 15 mg L^?1. © 2017 Society of Chemical Industry     

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

An approach to achieve confined crystallization of ferroelectric semicrystalline poly(vinylidene fluoride) (PVDF) was investigated. A novel polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene (PDMS‐b‐PMMA‐b‐PS) triblock copolymer was synthesized by the atom‐transfer radical polymerization method and blended with PVDF. Miscibility, crystallization and morphology of the PVDF/PDMS‐b‐PMMA‐b‐PS blends were studied within the whole range of concentration. In this A‐b‐B‐b‐C/D type of triblock copolymer/homopolymer system, crystallizable PVDF (D) and PMMA (B) middle block are miscible because of specific intermolecular interactions while A block (PDMS) and C block (PS) are immiscible with PVDF. Nanostructured morphology is formed via self‐assembly, displaying a variety of phase structures and semicrystalline morphologies. Crystallization at 145 °C reveals that both α and β crystalline phases of PVDF are present in PVDF/PDMS‐b‐PMMA‐b‐PS blends. Incorporation of the triblock copolymer decreases the degree of crystallization and enhances the proportion of β to α phase of semicrystalline PVDF. Introduction of PDMS‐b‐PMMA‐b‐PS triblock copolymer to PVDF makes the crystalline structures compact and confines the crystal size. Moreover, small‐angle X‐ray scattering results indicate that the immiscible PDMS as a soft block and PS as a hard block are localized in PVDF crystalline structures. © 2019 Society of Chemical Industry     

Preparation of star polymers of hyperbranched polyglycerol core with multiarms of PS‐b‐PtBA and PS‐b‐PAA

Atom transfer radical polymerization (ATRP) was applied to synthesize a new kind of star polymers of hyperbranched polyglycerol (HPG) core with multiarms of PS‐b‐PtBA and PS‐b‐PAA by using the “core first” technique. The HPG core was obtained by anionic polymerization of glycerol first, and then the pendant hydroxyl groups of HPG were esterified with 2‐bromoisobutyryl bromide to yield the HPG‐g‐Br, which was used as macroinitiator for ATRP of the first monomer (St) and then second monomer (tBA). After hydrolysis of the PtBA block, poly(acrylic acid) (PAA) side chains were formed. The final products and intermediates were characterized by GPC, NMR, and FTIR in detail. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry     

Controllable self‐assembly of polystyrene‐block‐poly(2‐vinylpyridine)

Block copolymers can form various ordered structures by self‐assembly, and their composites with inorganic materials may give surprising properties. This review summarizes recent developments in the preparation, mechanism and application of various types of self‐assembly of polystyrene‐block‐poly(2‐vinylpyridine) (PS‐b‐P2VP). The focus of the review is on how to control the self‐assembly of the dynamic and ordered structure of PS‐b‐P2VP based materials by applying effective factors such as thermal annealing, solvent annealing, block composition and blending. Moreover, the combination of the self‐assembly of PS‐b‐P2VP and various nanoparticles, with potentials in drug delivery, sensors and catalysis, is highlighted. © 2018 Society of Chemical Industry     

Preparation of well‐defined block copolymer having one polystyrene segment and another poly(styrene‐alt‐maleic anhydride) segment with RAFT polymerization

Block copolymers, polystyrene‐b‐poly(styrene‐co‐maleic anhydride), have been prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization technique using three different approaches: 1‐phenylethyl phenyldithioacetate (PEPDTA) directly as RAFT agent, mediated polystyrene (PS) block as the macromolecular PS‐RAFT agent and mediated poly(styrene‐maleic anhydride) (SMA) block with alternating sequence as the macromolecular SMA‐RAFT agent. Copolymers synthesized in the one‐step method using PEPDTA as RAFT agent possess one PS block and one SMA block with gradient structure. When the macromolecular RAFT agents are employed, copolymers with one PS block and one alternating SMA block can be produced. However, block copolymers with narrow molecular weight distribution (MWD) can only be obtained using the PS‐RAFT agent. The MWD deviates considerably from the typical RAFT polymerization system when the SMA is used as the RAFT agent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of polystyrene/poly(4‐vinylpyridine) triblock copolymers by reversible addition–fragmentation chain transfer polymerization and their self‐assembled aggregates in water

Reversible addition–fragmentation chain transfer polymerization (RAFT) was developed for the controlled preparation of polystyrene (PS)/poly(4‐vinylpyridine) (P4VP) triblock copolymers. First, PS and P4VP homopolymers were prepared using dibenzyl trithiocarbonate as the chain transfer agent (CTA). Then, PS‐b‐P4VP‐b‐PS and P4VP‐b‐PS‐b‐P4VP triblock copolymers were synthesized using as macro‐CTA the obtained homopolymers PS and P4VP, respectively. The synthesized polymers had relatively narrower molecular weight distributions (M_w/M_n < 1.25), and the polymerization was controlled/living. Furthermore, the polymerization rate appeared to be lower when styrene was polymerized using P4VP as the macro‐CTA, compared with polymerizing 4‐vinylpyridine using PS as the macro‐CTA. This was attributed to the different transfer constants of the P4VP and PS macro‐CTAs to the styrene and the 4‐vinylpyridine, respectively. The aggregates of the triblock copolymers with different compositions and chain architectures in water also were investigated, and the results are presented. Reducing the P4VP block length and keeping the PS block constant favored the formation of rod aggregates. Moreover, the chain architecture in which the P4VP block was in the middle of the copolymer chain was rather favorable to the rod assembly because of the entropic penalty associated with the looping of the middle‐block P4VP to form the aggregate corona and tailing of the end‐block PS into the core of the aggregates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1017–1025, 2003     

Synthesis and light‐emitting properties of a novel π‐conjugated poly[di(p‐phenyleneethynylene)‐alt‐ (p‐phenylenecyanovinylene)] containing n‐octyloxy side branches

A novel π‐conjugated poly[di(p‐phenyleneethynylene)‐alt‐(p‐phenylenecyanovinylene)] having n‐octyloxy side chains (PPE‐C₈PPE‐PPV) was prepared by polymerization of the monomer DEDB with BCN. Chemical structure of the polymer obtained was confirmed by ¹H NMR, FTIR, and EA. PPE‐C₈PPE‐PPV had a molecular weight enough to fabricate the electroluminescent (EL) device, and showed a good organosolubility, excellent thermal stability, and film‐forming property. In UV absorption and PL spectra in film it showed a maximum at 430 and 543 nm, respectively, which appeared 5 and 41 nm longer wavelengths than that of the solution, respectively. HOMO, LUMO energy levels and band gap were determined to be ?5.70, ?3.29, and 2.41 eV, respectively. Two EL devices with low‐work function cathodes were fabricated with the structures of ITO/PEDOT/PPE‐C₈PPE‐PPV/cathodes (LiF/Al and Mg:Ag/Ag). The both devices exhibited a bright green light emission at 545 nm and the maximum luminescence of 197 cd/cm² (LiF/Al) and 158 cd/cm² (Mg:Ag/Ag). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polystyrene‐block‐polylactide obtained by the combination of atom transfer radical polymerization and ring‐opening polymerization with a commercial dual initiator

A polystyrene (PS)‐b‐polylactide (PLA) block copolymer was prepared from the combination of atom transfer radical polymerization and ring‐opening polymerization with commercially available 2,2,2‐tribromoethanol as a dual initiator in a sequential two‐step procedure. Hydroxyl‐terminated polystyrene (PS‐OH)s with various molecular weights were first prepared with polydispersity indices lower than 1.3; these provided valuable macroinitiators for the polymerization of D,L ‐lactide. A block copolymer with a composition allowing the formation of hexagonally packed PLA cylinders in a PS matrix was then obtained. The PS‐b‐PLA thin films revealed, after vapor solvent annealing, a hexagonally packed organization of the PLA cylinders, which was oriented perpendicularly to the surface of the film. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Ab initio emulsion RAFT polymerization of vinylidene chloride mediated by amphiphilic macro‐RAFT agents

An amphiphilic copolymer poly(acrylic acid)‐block‐poly(styrene) (PAA‐b‐PS) with a trithiocarbonate reactive group was used in the ab initio reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization of vinylidene chloride (VDC). The fast polymerization and high conversion were achieved. The parameters for a good control over the formation of well‐defined PAA‐b‐PS‐b‐PVDC amphiphilic block copolymers and self‐stabilized latexes were identified. To improve the emulsion stability and prevent the desorption of water‐soluble initiating radicals, the acid groups of PAA‐b‐PS were neutralized by NaOH at the later stage of polymerization. The PAA‐b‐PS‐b‐PVDC block copolymer with a high molar mass of 30 kg mol⁻¹ and the stable latex with 30 wt % solid content was obtained. The kinetics of RAFT emulsion copolymerization of VDC in a living manner was first investigated. The as‐prepared PAA‐b‐PS‐b‐PVDC latex particles were further used as seeds in the emulsion polymerization of styrene, enabling the preparation of novel PAA‐b‐PS‐b‐PVDC‐b‐PS tetra‐block copolymers with a molar mass of 76 kg mol⁻¹ and a relatively low molecular weight distribution of 1.6. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40391.     

Preparation,characterization, and thermal properties of polystyrene‐block‐quaternized poly(4‐vinylpyridine)/Montmorillonite nanocomposites

Polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) was synthesized by two steps of reversible addition‐fragmentation transfer (RAFT) polymerization of styrene (St) and 4‐vinylpyridine (4VP) successively. After P4VP block was quaternized with CH₃I, PS‐b‐quaternized P4VP/montmorillonite (PS‐b‐QP4VP/MMT) nanocomposites were prepared by cationic exchange reactions of quaternary ammonium ion in the PS‐b‐QP4VP with ions in MMT. The results obtained from X‐ray diffraction (XRD) and transmission electron microscopy (TEM) images demonstrate that the block copolymer/MMT nanocomposites are of intercalated and exfoliated structures, and also a small amount of silicates' layers remained in the original structure; differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) results show that the nanocomposites displayed higher glass transition temperature (T_g) and higher thermal stability than that of the corresponding copolymers. The blending of PS‐b‐QP4VP/MMT with commercial PS makes MMT to be further separated, and the MMT was homogeneously dispersed in the polymer matrix. The enhancement of thermal stability of PS/PS‐b‐QP4VP/MMT is about 20°C in comparison with commercial PS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1950–1958, 2006     

Toughening of epoxy thermosets with polystyrene‐block‐polybutadiene‐block‐ polystyrene triblock copolymer via formation of nanostructures

In this contribution, we reported to utilize polystyrene‐block‐polybutadiene‐block‐polystyrene (PS‐b‐PB‐b‐PS), a commercial triblock copolymer to toughen epoxy thermosets. First, a PS‐b‐PB‐b‐PS triblock copolymer was chemically modified with hydroboration‐oxidation reaction, with which the midblock was hydroxylated whereas the endblocks remained unaffected. It was found that the degree of hydroxylation was well controlled. One of the hydroxylated PS‐b‐PB‐b‐PS samples was then used as the macromolecular initiator to synthesize a poly(ε‐caprolactone)‐grafted PS‐b‐PB‐b‐PS via the ring‐opening polymerization. It was found that the PS‐b‐PB‐b‐PS with poly(ε‐caprolactone) grafts can be successfully employed to nanostructure epoxy thermosets; the “core‐shell” microdomains composed of PB and PS were generated in the nanostructured thermosets. The nanostructured thermosets displayed improved fracture toughness. POLYM. ENG. SCI., 59:2387–2396, 2019. © 2019 Society of Plastics Engineers     

Synthesis,photo‐, and electroluminescent properties of the soluble poly[(2,5‐diphenylene‐1,3,4‐oxadiazole)‐ 4,4′‐vinylene]

A novel soluble conjugated polymer, poly[(2,5‐diphenylene‐1,3,4‐oxadiazole)‐4,4′‐vinylene] (O‐PPV), containing an electron‐transporting group on the main chain of PPV, was synthesized according to HORNER mechanism. The oligo‐polymer with M_w = 1000 and T_d = 270°C is soluble in chloroform and tetrahydrofuran. The photoluminescent (PL) properties were investigated using different concentrations of solid‐state O‐PPV/PEO blends absorption and selective excitation measurements. The results show that PL arises from interchain charge‐transfer states in solid‐state O‐PPV. Compared with the analogous single‐layer device constructed with PPV (ITO/PPV/Al), which emits two peaks at λ = 520 nm and 550 nm (shoulder), the electroluminescence (EL) spectrum of the device [ITO/O‐PPV (80 nm)/Al] is a broad peak at λ_max = 509 nm. The quantum efficiency (0.13%) of the device ITO/O‐PPV/Al is much higher than that of the device ITO/PPV/Al, due to the introduction of the electron‐transporting group–oxadiazole units in the main chain of PPV. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3535–3540, 1999     

Effect of cross‐linker on morphology,catalytic activity,and recyclability of immobilized palladium chloride

Two kinds of immobilized palladium (Pd) catalysts were prepared by reversible addition fragmentation chain transfer polymerization of pyridine‐containing monomer followed by immobilizing palladium chloride (PdCl₂) on block copolymers. Namely, one of them includes the cross‐linking structure of maleic anhydride with 1,6‐diaminohexane (cross‐linker), polystyrene‐block‐poly(4‐(4‐vinylbenzyloxy)butylpicolinate‐alt‐maleic anhydride)‐Pd (PS‐b‐P(VBP‐alt‐MAn)‐Pd), and the other is its non‐cross‐linking counterpart, polystyrene‐block‐poly(4‐(4‐vinylbenzyloxy) butylpicolinate)‐Pd (PS‐b‐PVBP‐Pd). From transmission electron microscopy images, it could be observed that they both assembled into micelles in the selective solvents. The Pd of PS‐b‐P(VBP‐alt‐MAn)‐Pd located in the core of micelles, whereas the Pd of PS‐b‐PVBP‐Pd was on the shell of the micelles. The PS‐b‐P(VBP‐alt‐MAn)‐Pd can be continuously used for five times without any appreciable loss of activity in the aqueous Suzuki‐coupling reaction. However, the catalytic activities of the PS‐b‐PVBP‐Pd decreased sharply with the increase in the recycle times. Thus, this promising cross‐linking strategy not only greatly restrained the loss of Pd in the catalytic cycles, but also effectively maintained the immobilized Pd catalyst's high activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Self‐organized MEH‐PPV domains in a TPU matrix and the consequences to the luminescence spectra

Self‐sustained cast films formed from heterogeneous blends of poly(2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenylenevinylene) (MEH‐PPV) conjugated polymer and thermoplastic polyurethane (TPU) were investigated by photoluminescence (PL) and scanning electron microscopy (SEM). A blue shift is observed for the pure electronic transition PL peak (E₀₀) with decreasing MEH‐PPV concentration. The two clear shoulders in the PL spectra at higher energy than the E₀₀ peak appear due to the formation of small conjugation segments of the MEH‐PPV molecules at the interface of the spherical MEH‐PPV domains. This assumption and the origin of the blue shift were confirmed by correlating the average size of the MEH‐PPV domains, observed from SEM images, and the analysis of the PL spectra at low temperatures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of poly(styrene‐b‐2‐hydroxyethyl acrylate) block copolymer using reverse iodine transfer polymerization

Reverse iodine transfer polymerizations (RITP) of 2‐h‐ydroxyethyl acrylate (HEA) were performed in N,N‐dimethylformamide at 75°C using AIBN as initiator. Poly(2‐hydroxyethyl acrylate) (PHEA) with M_n = 3300 g mol^?1 and M_w/M_n <1.5 were obtained. Homopolymerization of styrene in RITP was also carried out under similar conditions using toluene as solvent. The resulting iodo‐polystyrene (PS‐I) with (M_{n, SEC} = 607 g mol^?1, polydispersity index (PDI) = 1.31) was used as a macroinitiator for the synthesis of amphiphilic block copolymers based on HEA with controlled well‐defined structure. Poly(styrene‐b‐2‐hydroxyethyl acrylate) (PS‐b‐PHEA) with M_n = 13,000 g mol^?1 and polydispersity index (M_w/M_n) = 1.4 was obtained, copolymer composition was characterized using ¹H‐NMR and FTIR, whereas SEC and gradient HPLC were used to confirm the formation of block copolymer and the living character of polymer chains. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Compatibilizing efficiency of copolymer precursors for immiscible polymer blends

An anhydride‐terminated polystyrene (PS‐b‐Anh) as a block copolymer precursor and a copolymer (PS‐co‐TMI) of styrene (St) and 3‐isopropenyl‐α,α‐dimethylbenzene isocyanate (TMI) as a graft copolymer precursor are chosen to investigate the effect of the type of the copolymer precursor on its compatibilizing and stabilizing efficiency for polymer blends. Results show that during the melt blending of the PS and PA6, the addition of PS‐b‐Anh dramatically decreases the size of the dispersed phase domains, irrespective of its molecular weight. This indicates that a diblock copolymer PS‐block‐PA6 (PS‐b‐PA6) is formed by a reaction between the terminal anhydride moiety of the PS‐b‐Anh and the terminal amine group of the PA6. When PS/PA6 (30/70) blends are annealed at 230°C for 15 min, their morphologies are much more stable in the presence of the PS‐b‐Anh block copolymer precursor than in the presence of the PS‐co‐TMI graft copolymer precursor. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of polystyrene/poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] fluorescent microspheres by miniemulsion polymerization

Fluorescent microspheres have great potential for use as probes in biological diagnostics. In this context, poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] (MEH‐PPV), a conjugated polymer which has high quantum yield, controllable emitting wavelength and facile processing in manufacture, was used as a fluorescent material for the preparation of polystyrene (PS)/MEH‐PPV fluorescent microspheres via miniemulsion polymerization. We demonstrate that the emitting wavelength of the PS/MEH‐PPV fluorescent microspheres can be regulated by changing the amount of azobisisobutyronitrile initiator in the polymerization process. Using acrylic acid comonomer, poly[styrene‐co‐(acrylic acid)]/MEH‐PPV fluorescent microspheres with functional carboxyl groups were also prepared. All the microspheres were characterized using transmission electron microscopy, scanning electron microscopy, fluorescence microscopy and fluorescence spectrophotometry. The functional carboxyl groups were characterized using Fourier transform infrared spectroscopy. This work provides a novel platform for the preparation of conjugated polymer fluorescent microspheres for biological applications. © 2012 Society of Chemical Industry     

Architecture of nanostructured polymers by segregated domain crosslinking of block‐graft copolymer micelles

Polystyrene‐block‐polyisoprene (PS‐block‐PI; high 3,4‐structure) diblock copolymer was prepared by living anionic polymerization. For transfer into a reactive intermediate, the hydroxylation of the double bonds of PI block was achieved by hydroboration, followed by oxidation. Esterification of the hydroxy‐derivative with stearoyl chloride or decanoyl chloride resulted in block‐graft copolymers composed of PS (flexible chain)‐grafted long alkane (stretched chains). After partial chloromethylation of PS block copolymer, photofunctional N,N‐diethyldithiocarbamate (DC) groups were introduced into such pendant sites by reaction with the corresponding sodium salt. We studied the self‐assemblies of photofunctional block‐graft copolymers in a selective solvent, such as heptane, and constructed nanostructured polymers by crosslinking PS cores under UV irradiation. © 2001 Society of Chemical Industry     

Influence of PS‐b‐PEO diblock copolymers on the compatibility of syndiotactic polystyrene modified epoxy blends

Homogeneous solutions of syndiotactic polystyrene (sPS) in diglycidylether of bisphenol A (DGEBA), containing 2.5, 5 and 7.5 wt % of thermoplastic with or without 0.5 and 1 wt % of poly(styrene‐b‐ethylene oxide) (PS‐b‐PEO) block copolymer, were polymerized using a stoichiometric amount of an aromatic amine hardener, 4,4′‐methylene bis (3‐chloro‐2,6‐diethylaniline) (MCDEA). The dynamic‐mechanical properties and morphological changes of sPS‐(DGEBA/MCDEA) compatibilized with different amount of PS‐b‐PEO have been investigated in this paper. The addition of the block copolymer produced significant changes in the morphologies generated. The size of the dispersed spherical sPS spherulites does not change significantly, but less spherulites of sPS appeared upon network formation in the systems with compatibilizer, what means that addition of compatibilizer in this system delayed crystallization of sPS in sPS‐(DGEBA/MCDEA) systems and change phase separation mechanism from crystallization‐induced phase separation (CIPS) and reaction‐induced phase separation (RIPS) almost only to RIPS. Moreover, PS‐b‐PEO with higher molecular weight of PS block seems to be a more effective compatibilizer than one with lower molecular weight of PS block. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 479–488, 2006