MesoDyn simulation study on the phase morphologies of miktoarm PS‐b‐PMMA copolymer doped by nanoparticles

The compatibility of six groups 12 miktoarm polystyrene‐block‐poly(methyl methacrylate) copolymers is studied at 383, 413, and 443 K via mesoscopic modeling. The values of the order parameters depend on both the architectures of the block copolymers and the simulation temperature, whereas the change tendency of the order parameters is nearly the same at 413 and 443 K. Obviously, temperature presents more obvious effect on long and PMMA‐rich chains. A study of plain copolymers doped with nanoparticles shows that the microscopic phase is influenced by not only the properties of the nanoparticles, such as the size, number, and density, but also by the composition and architecture of copolymers. Increasing the size and the number of the nanoparticles used as a dopant plays the most significant role on the phase morphologies of the copolymers at lower and higher temperatures, respectively. Especially, the 13214‐type copolymers, which are PMMA‐rich composition, present microscopic phase separation as varying degrees of lamellar phase morphologies at 443 K, alternated with PS and PMMA component. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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 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     

Soft nanoconfinement effects on the crystallization behavior of asymmetric poly(ethylene oxide)‐block‐poly(ε‐ caprolactone) diblock copolymers

The time‐ and temperature‐related crystallization process for the structure transitions of asymmetric crystalline‐crystalline diblock copolymers from the melt to crystallites was investigated with synchrotron simultaneous small‐angle/wide‐angle X‐ray scattering. Two asymmetric poly(ethylene oxide)‐poly(ε‐caprolactone) diblock copolymers were chosen. It is found in the course of the copolymer crystallization that the shorter blocks are uncrystallizable in both of the asymmetric diblock copolymers and final lamellar structures are formed in both of them. The final lamellar structure was confirmed from atomic force microscopy observations. The small‐angle X‐ray scattering data collected were analyzed with different methods for the early stage of crystallization. Guinier and Debye‐Bueche plots indicate that there are neither isolated domains nor correlated domains formed before the formation of lamellae in the asymmetric diblock copolymers during the crystallization process. The structure evolution was calculated according to the correlation function, and the soft nanoconfined crystallization behavior is discussed. Copyright © 2012 Society of Chemical Industry     

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     

Synthesis and characterization of poly[(R,S)‐3‐hydroxybutyrate] telechelics and their use in the synthesis of poly(methyl methacrylate)‐b‐ poly(3‐hydroxybutyrate) block copolymers

Poly[(R,S)‐3‐hydroxybutyrate] oligomers containing dihyroxyl (PHB‐diol), dicarboxylic acid (PHB‐diacid) and hydroxyl‐carboxylic acid (a‐PHB) end functionalities were obtained by the anionic polymerization of β‐butyrolacton (β‐BL). Ring opening anionic polymerization of β‐BL was initiated by a complex of 18‐Crown‐6 with γ‐hydroxybutyric acid sodium salts (for PHB‐diol and a‐PHB) or succinic acid disodium salt (for PHB‐diacid). Dihydroxyl functionalization was formed by the termination of polymerization with bromo‐ethanol or bromo‐decanol while the others were done by protonation. Hydroxyl and/or carboxylic acid functionalized PHB oligomers with ceric salts were used to initiate the polymerization of methylmethacrylate (MMA). PHB‐b‐PMMA block copolymers obtained by this way were purified by fractional precipitation and characterized using ¹H‐NMR and ¹³C‐NMR, gel permeation chromatography (GPC), and thermal analysis (DSC and TGA) techniques. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 965–973, 2002     

Synthesis,characterization, and application of novel amphiphilic poly(D‐gluconamidoethyl methacrylate)‐b‐polyurethane‐b‐ poly(D‐gluconamidoethyl methacrylate) triblock copolymers

Novel amphiphilic ABA‐type poly(D ‐gluconamidoethyl methacrylate)‐b‐polyurethane‐b‐poly(D ‐gluconamidoethyl methacrylate) (PGAMA‐b‐PU‐b‐PGAMA) tri‐block copolymers were successfully synthesized via the combination of the step‐growth and copper‐catalyzed atom transfer radical polymerization (ATRP). Dihydroxy polyurethane (HO‐PU‐OH) was synthesized by the step‐growth polymerization of hexamethylene diisocyanate with poly(tetramethylene glycol). PGAMA‐b‐PU‐b‐PGAMA block copolymers were synthesized via copper‐catalyzed ATRP of GAMA in N, N‐dimethyl formamide at 20°C in the presence of 2, 2′‐bipyridyl using Br‐PU‐Br as macroinitiator and characterized by ¹H‐NMR spectroscopy and GPC. The resulting block copolymer forms spherical micelles in water as observed in TEM study, and also supported by ¹H NMR spectroscopy and light scattering. Miceller size increases with increase in hydrophilic PGAMA chain length as revealed by DLS study. The critical micellar concentration values of the resulting block copolymers increased with the increase of the chain length of the PGAMA block. Thermal properties of these block copolymers were studied by thermo‐gravimetric analysis, and differential scanning calorimetric study. Spherical Ag‐nanoparticles were successfully synthesized using these block copolymers as stabilizer. The dimension of Ag nanoparticle was tailored by altering the chain length of the hydrophilic block of the copolymer. A mechanism has been proposed for the formation of stable and regulated Ag nanoparticle using various chain length of hydrophilic PGAMA block of the tri‐block copolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Long‐term investigation on hydrolytic degradation and morphology of poly(ethylene glycol terephthalate)‐b‐poly(butylene terephthalate) copolymer films

Poly(ethylene glycol terephthalate)‐b‐Poly(butylene terephthalate) copolymer (PEGT‐b‐PBT) films with different copolymer compositions were incubated in phosphate buffered saline under pH 7.4 at 37°C to study hydrolytic degradation and morphology up to 300 days. With the fall of intrinsic viscosity and mass of degraded films, SEM micrographs show that a set of particular and highly interconnected porous morphologies closely related to the content of PBT hard segments in copolymer is developed. Moreover, the variation in PBT crystallinity for copolymer films with weight ratio of 70/30 fluctuates with the development of degradation profiles, and PEGT content for copolymer films with weight ratio of 80/20 and 70/30 gradually decreases. The hydrolytic experiments demonstrate that the degradation of PEGT‐b‐PBT copolymer results from the cleavage of ester bonds between hydrophilic PEG and terephthalate. At the beginning period of degradation, PEGT‐b‐PBT copolymer films follow a typical mechanism of bulk degradation, and then undergo both bulk degradation and surface erosion, all of which finally generate the particular porous morphologies for copolymer films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nonlinear phase‐separation behavior of poly(methyl methacrylate)/poly(styrene‐co‐maleic anhydride) blends

The nonlinear phase‐separation behavior of poly(methyl methacrylate)/poly(styrene‐co‐maleic anhydride) (PMMA/SMA) blends over wide appropriate temperature and heating rate ranges was studied using time‐resolved small‐angle laser light scattering. During the non‐isothermal process, a quantitative logarithm function was established to describe the relationship between cloud point (T_c) and heating rate (k) as given by T_c = Alnk + T₀, in which the parameter A, reflecting the heating rate dependence, is much different for different compositions due to phase‐separation rate and activation energy difference. For the isothermal phase‐separation process, an Arrhenius‐like equation was successfully applied to describe the temperature dependence of the apparent diffusion coefficient (D_app) and the relaxation time (τ) of the early stage as well as the late stage of spinodal decomposition (SD) of PMMA/SMA blends. Based on the successful application of the Arrhenius‐like equation, the related activation energies could be obtained from D_app and τ of the early and late stages of SD, respectively. In addition, these results indicate that it is possible to predict the temperature dependence of the phase‐separation behavior of binary polymer mixtures during isothermal annealing over a range of 100 °C above the glass transition temperature using the Arrhenius‐like equation. © 2012 Society of Chemical Industry     

A novel method for preparing silver/poly(siloxane‐b‐methyl methacrylate) nanocomposites with multiple properties in the DMF‐toluene mixture solvent

A novel method for preparing silver/poly(siloxane‐b‐methyl methacrylate) (Ag/(PDMS‐b‐PMMA)) hybrid nanocomposites was proposed by using the siloxane‐containing block copolymers as stabilizer. The reduction of silver nitrate (AgNO₃) was performed in the mixture solvent of dimethyl formamide (DMF) and toluene, which was used to dissolve double‐hydrophobic copolymer, as well as served as the powerful reductant. The presence of the PMMA block in the copolymer indeed exerted as capping ligands for nanoparticles. The resultant nanocomposites exhibited super hydrophobicity with water contact angle of 123.3^° and the thermogravimetry analysis (TGA) revealed that the resultant nanocomposites with more PDMS were more heat‐resisting. Besides, the antimicrobial efficiency of the most desirable nanocomposite (Ag/PDMS₆₅‐b‐PMMA₃₀ loaded with 7.3% silver nanoparticle) could reach up to 99.4% when contacting with escherichia coli within 120 min. As a whole, the resultant nanocomposites by the integration of excellent properties of silver nanoparticles as well as siloxane‐block copolymers can be a promising for the development of materials with hydrophobic, heat‐resisting and outstanding antibacterial properties from the chemical product engineering viewpoint. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4780–4793, 2013     

Synthesis of star‐shaped poly(ε‐caprolactone)‐b‐poly(L‐lactide) copolymers: From star architectures to crystalline morphologies

Hexa‐armed star‐shaped poly(ε‐caprolactone)‐block‐poly(L ‐lactide) (6sPCL‐b‐PLLA) with dipentaerythritol core were synthesized by a two‐step ring‐opening polymerization. GPC and ¹H NMR data demonstrate that the polymerization courses are under control. The molecular weight of 6sPCLs and 6sPCL‐b‐PLLAs increases with increasing molar ratio of monomer to initiator, and the molecular weight distribution is in the range of 1.03–1.10. The investigation of the melting and crystallization demonstrated that the values of crystallization temperature (T_c), melting temperature (T_m), and the degree of crystallinity (X_c) of PLLA blocks are increased with the chain length increase of PLLA in the 6sPCL‐b‐PLLA copolymers. On the contrary, the crystallization of PCL blocks dominates when the chain length of PLLA is too short. According to the results of polarized optical micrographs, both the spherulitic growth rate (G) and the spherulitic morphology are affected by the macromolecular architecture and the length of the block chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and surface characterization of poly(methyl methacrylate)‐block‐polydimethylsiloxane copolymers from macroazoinitiator

Poly(methyl methyacrylate)‐block‐polydimethylsiloxane (PMMA‐b‐PDMS) copolymers with various compositions were synthesized with PDMS‐containing macroazoinitiator (MAI), which was first prepared by a facile one‐step method in our lab. Results from the characterizations of X‐ray photoelectron spectroscopy (XPS), contact angle measurements, and atomic force microscopy (AFM) showed that the copolymer films took on a gradient of composition and more PDMS segments enriched at the film surfaces, which then resulted in the low surface free energy and little microphase separation at the film surfaces. By contrast, transmission electron microscopy (TEM) analysis demonstrated that distinct microphase separation occurred in bulk. Slight crosslinking of the block copolymers led to much steady morphology and more distinct microphase separation, in particularly for copolymers with low content of PDMS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

Polymerization‐induced phase separations in branched poly(methyl methacrylate) synthesis

Methyl methacrylate and ethylene glycol dimethacrylate or 1,6‐hexanediol dimethacrylate (HDDMA) were copolymerized in the presence of a nonsolvent (heptane) for poly(methyl methacrylate) (PMMA) to examine the phenomenon of polymerization‐induced phase separations (PIPS) in branched PMMA synthesis. The process was dependent upon the amount of nonsolvent and crosslinker in the reaction mixture. Gel particles were obtained in the majority of phase‐separated systems, and their formation was promoted by the preferential partition of monomer and crosslinker into the precipitated polymer phase during the phase separation process. Experimental data showed that, because of its lower solubility parameter, HDDMA can be used as crosslinker to minimize gel particle formation in systems where PIPS is present. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1462–1468, 2005     

Reaction‐induced phase separation in hexamethylene diisocyanate‐based poly(propylene oxide)/poly(ethylene oxide) bi‐soft segment oligomers

Oligomeric bi‐soft segment isocyanate‐terminated polyurethanes (ITPUs) are semi‐finished materials crucial for the synthesis of various PU products like foams, thermoplastic parts, dispersions or elastomers. Incompatibilities and thus phase separation phenomena play an essential role in tailoring the properties of the final products. Therefore, a detailed knowledge of these phenomena is mandatory in order to design products with properties meeting the requirements of a given application. In this study the reaction‐induced phase separation during the formation of ITPUs by application of two partially miscible soft segments is presented. The physicochemical basics of this process as well as the extent of the resulting phase separation are discussed on the basis of the initial phase diagram of the reactants. Reaction monitoring by NCO content titration and UV–visible spectroscopy reveals a dependency between the onset of phase separation and conversion. It is found that an increase of the initial content of hexamethylene diisocyanate delays the onset of phase separation. Differential scanning calorimetry reveals further that the phase separation is a direct consequence of the incompatibility of the soft segments. Overall, the findings support the hypothesis that the mechanism and the extent of phase separation are closely related to the ternary phase diagram of the reactants. © 2018 Society of Chemical Industry     

Synthesis and characterization of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers with dibutylmagnesium as catalyst

Two series of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers were prepared by the ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) and dibutylmagnesium in 1,4‐dioxane solution at 70°C. The triblock structure and molecular weight of the copolymers were analyzed and confirmed by ¹H NMR, ¹³C NMR, FTIR, and gel permeation chromatography. The crystallization and thermal properties of the copolymers were investigated by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results illustrated that the crystallization and melting behaviors of the copolymers were depended on the copolymer composition and the relative length of each block in copolymers. Crystallization exothermal peaks (T_c) and melting endothermic peaks (T_m) of PEG block were significantly influenced by the relative length of PCL blocks, due to the hindrance of the lateral PCL blocks. With increasing of the length of PCL blocks, the diffraction and the melting peak of PEG block disappeared gradually in the WAXD patterns and DSC curves, respectively. In contrast, the crystallization of PCL blocks was not suppressed by the middle PEG block. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Self‐complementary multiple hydrogen bonding interactions increase the glass transition temperatures to supramolecular poly(methyl methacrylate) copolymers

We have prepared a series of poly(methyl methacrylate) (PMMA)‐based copolymers through free radical copolymerization of methyl methacrylate in the presence of 2‐ureido‐4[1H]‐pyrimidinone methyl methacrylate (UPyMA). The glass transition temperature was increased with the increase of UPyMA contents in PMMA copolymers due to strong self‐complementary multiple hydrogen bonding interactions of UPy moiety. The Fourier transform infrared and solid‐state NMR spectroscopic analyses provided positive evidence for the presence of multiple hydrogen bonds interaction of UPy moiety. Furthermore, the proton spin‐lattice relaxation time in the rotating frame [T_1ρ(H)] for the PMMA copolymers had a single value that was less than pure PMMA, indicating the smaller domain sizes in PMMA copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Kinetic study of emulsion copolymerization of ethyl methacrylate/lauryl methacrylate in propylene glycol,stabilized with poly(ethylene oxide)–block–polystyrene–block–poly(ethylene oxide) triblock copolymer

The kinetics of emulsion copolymerization of ethyl methacrylate (EMA)/lauryl methacrylate (LMA) in propylene glycol is very similar to the emulsion copolymerizations of water‐soluble monomers in water because of the high solubility of EMA/LMA in propylene glycol. The initial rate of polymerization depends only on initiator concentration and is not affected by either monomer concentration or stabilizer concentration. The overall rate of polymerization is only slightly dependent on monomer concentration and stabilizer concentration and is independent of initiator concentration. The final particle number density increases with increasing amount of stabilizer and decreases with increasing monomer concentration. The total surface area increases with stabilizer concentration and is not governed by either initiator concentration or monomer concentration. Homogeneous nucleation is the dominant mechanism of particle nucleation, as shown by the kinetic data on seeded polymerization and monomer partition behavior. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1691–1704, 2001     

Self‐assembly of poly(3‐hexyl thiophene)‐b‐poly(ethylene oxide) into cylindrical micelles in binary solvent mixtures

Asymmetric block copolymer based on regioregular poly(3‐hexyl thiophene) (P3HT) and poly(ethylene oxide) (PEO) was synthesized through Heck reactions. The addition of PEO block has no influence in the effective conjugation length of P3HT block and apparently provides colloidal stability for the formation of stable nanostructures. Introduction of poor solvent to good solvent containing P3HT‐b‐PEO will induce the crystallization‐driven assembly of the P3HT into cylindrical micelles with a P3HT core, owing to π–π stacking of the conjugated backbone of P3HT. The absorption spectra of the cylindrical micelles reveal a red shift as compared to the polymer in good solvent, indicating the extension of conjugation length with an improved π–π stacking of the polymer chains within the cylindrical micelles. Our results indicated that cylindrical micelles with varied diameter and length can be obtained when solvent properties were varied using several different binary solvent mixtures. More interestingly, we demonstrate that ultrasonic processing can fragment the cylindrical micelles only when the ratio of poor solvent increases. This provides a facile and effective way to fabricate cylindrical micelles for applications in the area of polymer solar cell as well as organic optoelectronics device. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41186.