Synthesis of water‐soluble polyphenol‐graft‐poly(ethylene oxide) copolymers via enzymatic polymerization and anionic polymerization

Water‐soluble polyphenol‐graft‐poly(ethylene oxide) (PPH‐g‐PEO) copolymers were prepared using grafting‐through methodology. Polyphenol chains were synthesized via enzymatic polymerization of phenols, and the graft chains were synthesized via living anionic polymerization of ethylene oxides. The polymers were characterized using gel permeation chromatography, static light scattering and ¹H NMR, infrared and ultraviolet spectroscopies. The PPH‐g‐PEO graft copolymers are soluble in several common solvents, such as water, ethanol, N,N‐dimethylformamide, tetrahydrofuran and methylene dichloride. The solubility of the PPH‐g‐PEO graft copolymers is improved significantly compared with that of polyphenol. Copyright © 2009 Society of Chemical Industry     

Synthesis and characterization of oligosalicylaldehyde‐graft‐oligoaniline and its beginning oligomers

Conjuge bonding oligosalicylaldehyde‐graft‐oligoaniline (OSA‐graft‐OA) was synthesized from the polycondensation reaction of oligosalicylaldehyde (OSA) with oligoaniline (OA). There were various functional groups such as ? OH, ? NH and ? CH?N in the structure of the graft cooligomer. The physical properties of graft‐co‐oligomers such as melting temperature and solubility were studied: number‐average molecular weight, mass‐average molecular weight, and a polydispersity index of OA, OSA, and fractions of the graft cooligomers [(OSA‐graft‐OA)‐I] and [(OSA‐graft‐OA)‐II] were found to be 740, 780 g mol^?1,1.05; 3700, 5990 g mol^?1, 1.62; 990, 2770 g mol^?1, 2.80 and 1300, 4100 g mol^?1, 3.15, respectively. The FTIR and UV‐Vis spectra of the graft cooligomer were compared with those of beginning oligomers. The spectral analyses results showed that the OSA‐graft‐OA synthesized from the polycondensation reaction of aromatic amine with aldehyde that have long oligophenol macromolecule bonded each other with an azomethine bridge through oligophenylamine side chains. The thermal stability of the graft cooligomer and oligomers were measured by thermogravimetric analysis (TG) under an air atmosphere. According to TG analyses, the carboneous residues of the [(OSA‐graft‐OA)‐I) (soluble in ethanol) and (OSA‐graft‐OA)‐II) (soluble in toluene)] were 23 and 40%, respectively, at 1000°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 218–226, 2002     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Preparation and characterization of amphiphilic block copolymer of polyacrylonitrile‐block‐poly(ethylene oxide)

The synthesis of polyacrylonitrile‐block‐poly(ethylene oxide) (PAN‐b‐PEO) diblock copolymers is conducted by sequential initiation and Ce(IV) redox polymerization using amino‐alcohol as the parent compound. In the first step, amino‐alcohol potassium with a protected amine group initiates the polymerization of ethylene oxide (EO) to yield poly(ethylene oxide) (PEO) with an amine end group (PEO‐NH₂), which is used to synthesize a PAN‐b‐PEO diblock copolymer with Ce(IV) that takes place in the redox initiation system. A PAN‐poly(ethylene glycol)‐PAN (PAN‐PEG‐PAN) triblock copolymer is prepared by the same redox system consisting of ceric ions and PEG in an aqueous medium. The structure of the copolymer is characterized in detail by GPC, IR, ¹H‐NMR, DSC, and X‐ray diffraction. The propagation of the PAN chain is dependent on the molecular weight and concentration of the PEO prepolymer. The crystallization of the PAN and PEO block is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1753–1759, 2003     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Poly(ethylene oxide)‐block‐polystyrene copolymers obtained by radical polymerization involving chain‐transfer processes

Poly(ethylene oxide)‐block‐polystyrene (PEO–PSt) block copolymers were prepared by radical polymerization of styrene in the presence of iodoacetate—terminated PEO (PEO‐I) as a macromolecular chain‐transfer agent. PEO‐I was synthesized by successively converting the OH end‐group of α‐methoxy ω‐hydroxy PEO to chloroacetate and then to the iodoacetate. The chain‐transfer constant of PEO‐I was estimated from the rate of consumption of the transfer agent versus the rate of consumption of the monomer (C_{tr, PEO‐I} = 0.23). Due to the involvement of degenerative transfer, styrene polymerization in the presence of PEO‐I displayed some of the characteristics of a controlled/‘living’ process, namely an increase in the molecular weight and decrease of polydispersity with monomer conversion. However, because of the slow consumption of PEO‐I due to its low chain‐transfer constant, this process was not a fully controlled one, as indicated by the polydispersity being higher than in a controlled polymerization process (1.65 versus < 1.5). The formation of PEO–PSt block copolymers was confirmed by the use of size‐exclusion chromatography and ¹H NMR spectroscopy. Copyright © 2004 Society of Chemical Industry     

Thiol–ene addition enables tailored synthesis of poly(2‐oxazoline)‐graft‐poly(vinyl pyrrolidone) copolymers for binder jetting 3D printing

The continued interest in graft copolymer architectures arises from their unique solution properties and potential for a myriad of applications ranging from drug delivery to adhesives. Poly(vinyl pyrrolidone) (PVP) represents a popular amorphous, water‐soluble polymer used as a polymeric binder in binder jetting additive manufacturing, as fillers in cosmetic products, and for subcutaneous drug delivery systems. This report describes the synthesis of poly(2‐oxazoline) and PVP graft copolymers using a ‘grafting to’ methodology with an efficient thiol–ene ‘click’ reaction. Copolymerization of 2‐methyl‐2‐oxazoline and 2‐(3‐butenyl)‐2‐oxazoline introduced pendent vinyl grafting sites with a predictable absolute number‐average molecular weight. In parallel, reversible addition‐fragmentation chain‐transfer polymerization and subsequent aminolysis yielded well‐defined, oligomeric, thiol‐terminated PVP. Thiol–ene click chemistry enabled the formation of poly(2‐oxazoline)‐graft‐poly(vinyl pyrrolidone) (PMeOx‐g‐PVP) copolymers with varying mole percent grafting sites and PVP graft length. ¹H NMR spectroscopy, aqueous SEC with multiangle light scattering (SEC‐MALS), and bromine titrations confirmed chemical structure, and DSC with TGA elucidated thermal transitions. Aqueous SEC‐MALS and ¹H NMR spectroscopy also determined absolute number‐ and weight‐average molecular weights and average grafting levels, which revealed optimal reaction conditions. Zero‐shear viscosities of 5 and 10 wt% solutions in deionized water for each graft copolymer compared to their linear analogs demonstrated a significant (ca 31%) decrease in viscosity at the same number‐average molecular weight. This decrease in solution viscosity suggested PMeOx‐g‐PVP copolymers as exceptional alternatives to linear analogs for aqueous‐based, binder jetting additive manufacturing.     

Surface modification of linear low‐density polyethylene film by amphiphilic graft copolymers based on poly(higher α‐olefin)‐graft‐poly(ethylene glycol)

In this article, a series of amphiphilic graft copolymers, namely poly(higher α‐olefin‐co‐para‐methylstyrene)‐graft‐poly(ethylene glycol), and poly(higher α‐olefin‐co‐acrylic acid)‐graft‐poly(ethylene glycol) was used as modifying agent to increase the wettability of the surface of linear low‐density polyethylene (LLDPE) film. The wettability of the surface of LLDPE film could be increased effectively by spin coating of the amphiphilic graft copolymers onto the surface of LLDPE film. The higher the content of poly(ethylene glycol) (PEG) segments, the lower the water contact angle was. The water contact angle of modified LLDPE films was reduced as low as 25°. However, the adhesion between the amphiphilic graft copolymer and LLDPE film was poor. To solve this problem, the modified LLDPE films coated by the amphiphilic graft copolymers were annealed at 110° for 12 h. During the period of annealing, heating made polymer chain move and rearrange quickly. When the film was cooled down, the alkyl group of higher α‐olefin units and LLDPE began to entangle and crystallize. Driven by crystallization, the PEG segments rearranged and enriched in the interface between the amphiphilic graft copolymer and air. By this surface modification method, the amphiphilic graft copolymer was fixed on the surface of LLDPE film. And the water contact angle was further reduced as low as 14.8°. The experimental results of this article demonstrate the potential pathway to provide an effective and durable anti‐fog LLDPE film. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on a new kind of polypropylene‐graft‐ polystyrene: Preparation and application

A novel synthetic route for preparing polypropylene‐graft‐polystyrene (PP‐g‐PSt) was set up. With this synthetic route, a series of PP‐g‐PSt copolymers containing different percentages of polystyrene chain were synthesized, based on the different reactivities of two kinds of C? C double bonds on 4‐(3‐butenyl) styrene. Characterization data, including ¹H‐NMR, ¹³C‐NMR, GPC, and DSC, demonstrated that the graft copolymers were all very pure. Furthermore, it was also attempted to use this new kind of propylene–styrene graft copolymer as a compatibilizer. DMA and SEM results illustrated that the PP‐g‐PSt obtained is an efficient compatibilizer for the polypropylene–polystyrene blend. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 314–322, 2004     

Poly(ethylene‐co‐vinyl acetate)‐graft‐poly(methyl methacrylate) (EVA‐graft‐PMMA) as a modifier of epoxy resins

Conventional approaches to toughen thermosets are: (1) the polymerization‐induced phase separation of a rubber or a thermoplastic, or (2) the use of a dispersion of preformed particles in the initial formulation. In the present study it is shown that it is possible to combine both techniques by using graft copolymers with one of the blocks being initially immiscible and the other that phase separates during polymerization. This is illustrated by the use of poly(ethylene‐co‐vinyl acetate)‐graft‐poly(methyl methacrylate) (EVA‐graft‐PMMA) as modifier of an epoxy resin. EVA is initially immiscible and PMMA phase separates during polymerization. Blends of an epoxy monomer based on diglycidylether of bisphenol A (DGEBA, 100 parts by weight), piperidine (5 parts by weight), and PMMA (5 parts by weight), showed the typical polymerization‐induced phase separation of PMMA‐rich domains before gelation of the epoxy network. Replacing PMMA by EVA‐graft‐PMMA (5 parts by weight), yielded stable dispersions of EVA blocks, favoured by the initial solubility of PMMA blocks. Phase separation of PMMA blocks in the course of polymerization led to a dispersion of in situ generated biphasic particles (plausibly composed of EVA cores surrounded by PMMA shells), with average diameters varying from 0.3 to 0.6 µm with the cure temperature. This procedure may be used to generate stable dispersions of biphasic particles for toughening purposes. © 2002 Society of Chemical Industry     

Synthesis and thermal properties of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) copolymers as novel solid–solid phase‐change materials for thermal energy storage

We synthesized a series of poly(acrylonitrile‐co‐allyl glycidyl ether)‐graft‐methoxypoly(ethylene glycol) (PAA‐g‐MPEG) copolymers as novel polymeric solid–solid phase‐change materials by grafting methoxypoly(ethylene glycol) (MPEG) to the main chain of poly(acrylonitrile‐co‐allyl glycidyl ether) (PAA). PAA was the skeleton, and MPEG was a functional side chain, which stored and released heat during its phase‐transition process. Fourier transform infrared spectroscopy and ¹H‐NMR spectroscopy analysis were performed to investigate the chemical structures. The crystalline morphology and crystal structures were also measured with polarized optical microscopy and X‐ray diffraction. Moreover, the thermal‐energy‐storage properties, thermal stability, and thermal reliability of the PAA‐g‐MPEG copolymers were characterized by differential scanning calorimetry and thermogravimetric analysis (TGA) methods. These analysis results indicate that the MPEG chains were successfully grafted onto PAA, and we found that the PAA‐g‐MPEG copolymers had typical solid–solid phase‐transition temperatures in the range 11–54 °C and high latent heat enthalpies between 44 and 85 J/g. In addition, the as‐prepared PAA‐g‐MPEG copolymers showed reusability and thermal reliability, as shown by the thermal cycle testing and TGA curves. Therefore, the synthesized PAA‐g‐MPEG copolymers have considerable potential for thermal energy storage. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46641.     

Synthesis and characterization of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers by atom‐transfer radical polymerization

Well‐defined polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐PS triblock copolymers were synthesized by atom‐transfer radical polymerization (ATRP), using C—X‐end‐group PEO as macroinitiators. The triblock copolymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The experimental results showed that the polymerization was controlled/living. It was found that when the number‐average molecular weight of the macroinititors increased from 2000 to 10,000, the molecular weight distribution of the triblock copolymers decreased roughly from 1.49 to 1.07 and the rate of polymerization became much slower. The possible polymerization mechanism is discussed. According to the Cu content measured with atomic absorption spectrometry, the removal of catalysts, with CHCl₃ as the solvent and kaolin as the in situ absorption agent, was effective. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2882–2888, 2000     

Synthesis and surface properties of polystyrene‐graft‐poly(ethylene glycol) copolymers

Polystyrene‐graft‐poly(ethylene glycol) copolymers (PS‐g‐PEG) were successfully synthesized using the “grafting‐through” method. The graft copolymers and the surface properties of their coats were characterized by 1 H‐NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), static contact angle measurement, and atomic force microscopy (AFM). Both DSC and TEM indicated that the graft copolymers had a microphase separated structure. AFM showed the microphase separated structure also occurred at the coat surface, especially at high PEG content, which could also be indirectly confirmed by the XPS and contact angle results. The formation mechanism of the microphase separated structure was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1458–1465, 2007     

Synthesis and characterization of thermo‐ and pH‐sensitive block copolymers bearing a biotin group at the poly(ethylene oxide) chain end

A poly(ethylene oxide)‐block‐poly(dimethylamino ethyl methacrylate) block copolymer (PEO‐b‐PDMAEMA) bearing an amino moiety at the PEO chain end was synthesized by a one‐pot sequential oxyanionic polymerization of ethylene oxide (EO) and dimethylamino ethyl methacrylate (DMAEMA), followed by a coupling reaction between its PEO amino and a biotin derivative. The polymers were charac terized with ¹H NMR spectroscopy and gel permeation chromatography. Activated biotin, biotin‐NHS (N‐hydroxysuccinimide), was used to synthesize biotin‐PEO‐PDMAEMA. In aqueous media, the solubility of the copolymer was temperature‐ and pH‐sensitive. The particle size of the micelle formed from functionalized block copolymers was determined by dynamic light scattering. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3552–3558, 2006     

Novel bioresorbable hydrogels prepared from chitosan‐graft‐polylactide copolymers

A series of biodegradable chitosan‐graft‐polylactide (CS‐g‐PLA) copolymers were prepared by grafting of poly(L ‐lactide) (PLLA) or poly(D ‐lactide) (PDLA) precursor to the backbone of chitosan using N,N′‐carbonyldiimidazole as coupling agent. The composition of the copolymers was varied by adjusting the chain length of PLA as well as the ratio of chitosan to PLA. The copolymers synthesized via this ‘graft‐onto’ method present interesting properties as shown by NMR and infrared spectroscopy, gel permeation chromatography and solubility tests. Hydrogels were prepared by mixing water‐soluble CS‐g‐PLLA and CS‐g‐PDLA solutions. Gelation was assigned to stereocomplexation between PLLA and PDLA blocks as evidenced by differential scanning calorimetry and wide‐angle X‐ray diffraction measurements. Thymopentin (TP5) was taken as a model drug to evaluate the potential of these CS‐g‐PLA hydrogels as drug carriers. An initial burst and a final release up to 82% of TP5 were observed from high‐performance liquid chromatography analysis. Copyright © 2011 Society of Chemical Industry     

Separation and characterization of poly(styrene‐co‐acrylonitrile)‐graft‐poly(propylene oxide) polymer stabilizer formed in dispersion polymerization of styrene and acrylonitrile in polyether

Poly(styrene‐co‐acrylonitrile)‐graft‐poly(propylene oxide) (PSAN‐graft‐PPO), the stabilizer formed in situ in the dispersion polymerization of styrene, acrylonitrile and macromonomer PPO maleate in PPO polyol, was separated from ungrafted copolymer PSAN by liquid chromatography. After the determination of the separation conditions by thin‐layer chromatography, the effective separation of the graft polymer from copolymer PSAN was achieved by liquid column chromatography. The graft efficiency and the composition of the graft polymer was determined by UV and ¹H NMR, and the formation characteristics of the graft polymer are discussed. © 2001 Society of Chemical Industry     

Synthesis and characterization of a novel amphiphilic poly (ethylene glycol)–poly (ε-caprolactone) graft copolymers

A series of amphiphilic graft copolymers PEO-g-PCL with different poly (ε-caprolactone) (PCL) molecular weight were successfully synthesized by a combination of anionic ring-opening polymerization (AROP) and coordination-insertion ring-opening polymerization. The linear PEO was produced by AROP of ethylene oxide (EO) and ethoxyethyl glycidyl ether initiated by 2-(2-methoxyethoxy) ethoxide potassium, and the hydroxyl groups on the backbone were deprotected after hydrolysis. The ring-opening polymerization of CL was initiated using the linear poly (ethylene oxide) (PEO) with hydroxyl group on repeated monomer as macroinitiator and Sn(Oct)₂ as catalyst, then amphiphilic graft copolymers PEO-g-PCL were obtained. By changing the ratio of monomer and macroinitiator, a series of PEO-g-PCL with well-defined structure, molecular weight control, and narrow molecular weight distribution were prepared. The expected intermediates and final products were confirmed by ¹H NMR and GPC analyzes. In addition, these amphiphilic graft copolymers could form spherical aggregates in aqueous solution by self-assemble, which were characterized by transmission electron microscopy, and the critical micelle concentration values of graft copolymers PEO-g-PCL were also examined in this article.     

Hyperbranched–linear–hyperbranched ABA‐type block copolymers based on poly(ethylene oxide) and polyglycerol

BACKGROUND: Until recently, hyperbranched polymers were thought to be ill‐defined materials that were not useful as building blocks for well‐defined complex polymer architectures. It is a current challenge to develop strategies that offer rapid access to well‐defined hyperbranched block copolymers. RESULTS: A convenient three‐step protocol for the synthesis of double‐hydrophilic hyperbranched–linear–hyperbranched ABA‐type triblock copolymers based on poly(ethylene oxide) (PEO) and hyperbranched polyglycerol (hbPG) is presented. The Bola‐type polymers exhibiting an aliphatic polyether structure were prepared from a linear (lin) linPG‐b‐PEO‐b‐linPG precursor triblock. The materials exhibit low polydispersities (M_w/M_n) in the range 1.19–1.45. The molecular weights of the block copolymers range from 6300 to 26 200 g mol^?1, varying in the length of both the linear PEO chain as well as the hbPG segments. Detailed characterization of the thermal properties using differential scanning calorimetry demonstrates nanophase segregation of the blocks. CONCLUSION: The first example of well‐defined ABA hyperbranched–linear–hyperbranched triblock copolymers with PEO middle block and hbPG A‐blocks is presented. The biocompatible nature of the aliphatic polyether blocks renders these materials interesting for biomedical purposes. These new materials are also intriguing with respect to their supramolecular order and biomineralization properties. Copyright © 2009 Society of Chemical Industry     

The preparation and characterization of high‐performance and thermally stable electroluminescent poly(p‐phenylene‐vinylene‐b‐oligoethylene oxide)

Two luminescent block copolymers (PPVPEO₂₀₀ and PPVPEO₆₀₀), composed of poly(p‐phenylene‐vinylene) (PPV) segments with three phenylene vinylene units and poly(ethylene oxide) (PEO) segments with molecular weight of 200 and 600, respectively, have been successfully synthesized. The structures of the copolymers were verified using FTIR, ¹H‐NMR, and elemental analysis. Single‐layer polymer light‐emitting electrochemical cells (LEC) devices fabricated on the bases of thin films of PPVPEO₆₀₀ and on the bases of thin films of blends of PPVPEO₂₀₀ with additional PEO both demonstrated good electroluminescent (EL) performance with the onset voltage of 2.6 V and EL efficiency of 0.64 cd/A and 0.68 cd/A at 3.2 V, respectively. Thermal analysis shows that the decomposition temperature of PPVPEO₆₀₀ is about 305°C, which is higher than that of PPVPEO₂₀₀ and PEO. AFM studies of PPVPEO₆₀₀ thin films exhibits that the block copolymer self‐assembles to form nanoscale network structures with pseudo‐cross‐linking points, thus accounting for its high thermal stability and good EL performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1118–1125, 2007     

MesoDyn modeling study of the phase morphologies of miktoarm poly(ethylene oxide)‐b‐poly(methyl methacrylate) copolymers doped with nanoparticles

Earlier studies have shown that poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blocks are compatible at 270 and 298 K, and that their Flory–Huggins interaction parameters have the same blending ratio dependence at both temperatures. At a much higher temperature (400 K), the behavior of PEO/PMMA blends is strikingly different as both components become incompatible, while the Flory–Huggins parameters are low. Here we investigate the effect of doping with nanoparticles on the degree of incompatibility of twelve miktoarm PEO‐b‐PMMA copolymers at 400 K. Since PEO tends to be semicrystalline and long chains aggregate easily, PEO‐rich and long‐chain copolymer blends feature the highest degree of incompatibility for all nanoparticle arrangements and present cubic phase morphologies. In addition, the largest nanoparticles can reinforce the microscopic phase separation of all PEO‐b‐PMMA copolymers. This shows that the main factor affecting the phase morphology is the size of the nanoparticles. Also, only the asymmetric Da3‐type PEO‐rich copolymers show a hexagonal cylindrical phase morphology, which illustrates the effect induced by the nanoparticles on the microscopic phase separation changes of the PEO‐b‐PMMA copolymers. These induced effects are also related to the composition and molecular architecture of the copolymers. © 2013 Society of Chemical Industry