Microphase separation behavior on the surfaces of poly(dimethylsiloxane)‐block‐poly(2,2,3,3,4,4,4‐heptafluorobutyl methacrylate) diblock copolymer coatings

Microphase separation behavior on the surfaces of poly(dimethylsiloxane)‐block‐poly(2,2,3,3,4,4,4‐heptafluorobutyl methacrylate) (PDMS‐b‐PHFBMA) diblock copolymer coatings was investigated. The PDMS‐b‐PHFBMA diblock copolymers were successfully synthesized via atom transfer radical polymerization (ATRP). The chemical structure of the copolymers was characterized by nuclear magnetic resonance and Fourier transform infrared spectroscopy. Surface composition was studied by X‐ray photoelectron spectroscopy. Copolymer microstructure was investigated by atomic force microscopy. The microstructure observations show that well‐organized phase‐separated surfaces consist of hydrophobic domain from PDMS segments and more hydrophobic domain from PHFBMA segments in the copolymers. The increase in the PHFBMA content can strengthen the microphase separation behavior in the PDMS‐b‐PHFBMA diblock copolymers. And the increase in the annealing temperature can also strengthen the microphase separation behavior in the PDMS‐b‐PHFBMA diblock copolymers. Moreover, Flory‐Huggins thermodynamic theory was preliminarily used to explain the microphase separation behavior in the PDMS‐b‐PHFBMA diblock copolymers.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Synthesis and characterization of PS‐b‐PDMS‐b‐PS triblock copolymer

A series of polystyrene‐b‐poly(dimethylsiloxane)‐b‐polystyrene (PS/PDMS/PS) triblock copolymers had been synthesized by atom transfer radical polymerization (ATRP). The products had been characterized by Fourier transform infrared, gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, contact angle, and scanning electron microscope. The results indicate that the PS chains have been successfully blocked onto the PDMS back bone, and the PS‐b‐PDMS‐b‐PS triblock copolymers have low‐surface tension, good thermal stability, and microphase separation configuration. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and surface properties of polydimethylsiloxane‐based block copolymers: poly[dimethylsiloxane‐block‐ (ethyl methacrylate)] and poly[dimethylsiloxane‐block‐(hydroxyethyl methacrylate)]

A polydimethylsiloxane (PDMS) macroazoinitiator was synthesized from bis(hydroxyalkyl)‐terminated PDMS and 4,4′‐azobis‐4‐cyanopentanoic acid by a condensation reaction. The bifunctional macroinitiator was used for the block copolymerization of ethyl methacrylate (EMA) and 2‐(trimethylsilyloxy)ethyl methacrylate (TMSHEMA) monomers. The poly(DMS‐block‐EMA) and poly(DMS‐block‐TMSHEMA) copolymers thus obtained were characterized using Fourier transform infrared and ¹H NMR spectroscopy and differential scanning calorimetry. After the deprotection of trimethylsilyl groups, poly(DMS‐block‐HEMA) and poly(DMS‐block‐EMA) copolymer film surfaces were analysed using scanning electron microscopy and X‐ray photoelectron spectroscopy. The effects of the PDMS concentration in the copolymers on both air and glass sides of films were examined. The PDMS segments oriented and moved to the glass side in poly(DMS‐block‐EMA) copolymer film while orientation to the air side became evident with increasing DMS content in poly(DMS‐block‐HEMA) copolymer film. The block copolymerization technique described here is a versatile and economic method and is also applicable to a wide range of monomers. The copolymers obtained have phase‐separated morphologies and the effects of DMS segments on copolymer film surfaces are different at the glass and air sides. Copyright © 2010 Society of Chemical Industry     

The role of the ratio (PEG:PPG) of a triblock copolymer (PPG‐b‐PEG‐b‐PPG) in the cure kinetics,miscibility and thermal and mechanical properties in an epoxy matrix

The aim of this study was to evaluate the role of different poly(ethylene glycol):poly(propylene glycol) (PEG:PPG) molar ratios in a triblock copolymer in the cure kinetics, miscibility and thermal and mechanical properties in an epoxy matrix. The poly(propylene glycol)‐block‐poly(ethylene glycol)‐block‐poly(propylene glycol) (PPG‐b‐PEG‐b‐PPG) triblock copolymers used had two different molecular masses: 3300 and 2000 g mol^?1. The mass concentration of PEG in the copolymer structure played a key role in the miscibility and cure kinetics of the blend as well as in the thermal–mechanical properties. Phase separation was observed only for blends formed with the 3300 g mol^?1 triblock copolymer at 20 wt%. Concerning thermal properties, the miscibility of the copolymer in the epoxy matrix reduced the T_g value by 13 °C, although a 62% increase in fracture toughness (K_IC) was observed. After the addition of PPG‐b‐PEG‐b‐PPG with 3300 g mol^?1 there was a reduction in the modulus of elasticity by 8% compared to the neat matrix; no significant changes were observed in T_g values for the immiscible system. The use of PPG‐b‐PEG‐b‐PPG with 2000 g mol^?1 reduced the modulus of elasticity by approximately 47% and increased toughness (K_IC) up to 43%. Finally, for the curing kinetics of all materials, the incorporation of the triblock copolymer PPG‐b‐PEG‐b‐PPG delayed the cure reaction of the DGEBA/DDM (DGEBA, diglycidyl ether of bisphenol A; DDM, Q3‐4,4′‐Diaminodiphenylmethane) system when there is miscibility and accelerated the cure reaction when it is immiscible. All experimental curing reactions could be fitted to the Kamal autocatalytic model presenting an excellent agreement with experimental data. This model was able to capture some interesting features of the addition of triblock copolymers in an epoxy resin. © 2018 Society of Chemical Industry     

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     

Atomic force microscopy study of self‐assembly behaviors of hydrophobic poly(n‐butyl methacrylate)‐block‐polydimethylsiloxane‐block‐poly(n‐butyl methacrylate) ABA triblock copolymers

Poly(n‐butyl methacrylate)‐block‐polydimethylsiloxane‐block‐poly(n‐butyl methacrylate) (PBMA‐block‐PDMS‐block‐PBMA) ABA triblock copolymers were synthesized successfully via atom‐transfer radical polymerization using PDMS as macroinitiator. The effects of PDMS content and substrate nature on self‐assembly behaviors of PBMA‐block‐PDMS‐block‐PBMAs were systematically studied using atomic force microscopy. Two series of triblock copolymers with different molecular weights and compositions, i.e. PBMA‐block‐PDMSA12‐block‐PBMAs and PBMA‐block‐PDMSA21‐block‐PBMAs, were used, where the latter were of a higher PDMS content than the former. On silicon wafer, it was found that only spherical structures formed after annealing films spin‐coated from chloroform solutions of PBMA‐block‐PDMSA12‐block‐PBMAs. In contrast, films of PBMA‐block‐PDMSA21‐block‐PBMAs formed semi‐continuous structures. On mica wafer, it was found that ordered cylindrical pores formed after annealing films spin‐coated from chloroform solutions of PBMA‐block‐PDMSA12‐block‐PBMAs. In contrast, films of PBMA‐block‐PDMSA21‐block‐PBMAs formed isolated cylinders or worm‐like morphologies. Copyright © 2011 Society of Chemical Industry     

Morphology of poly(styrene‐block‐dimethylsiloxane) copolymer films

The morphologies of poly(styrene‐block‐di‐methylsiloxane) (PS‐b‐PDMS) copolymer thin films were analyzed via atomic force microscopy and transition electron microscopy (TEM). The asymmetric copolymer thin films spin‐cast from toluene onto mica presented meshlike structures, which were different from the spherical structures from TEM measurements. The annealing temperature affected the surface morphology of the PS‐b‐PDMS copolymer thin films; the polydimethylsiloxane (PDMS) phases at the surface were increased when the annealing temperature was higher than the PDMS glass‐transition temperature. The morphologies of the PS‐b‐PDMS copolymer thin films were different from solvent to solvent; for thin films spin‐cast from toluene, the polystyrene (PS) phase appeared as pits in the PDMS matrix, whereas the thin films spin‐cast from cyclohexane solutions exhibited an islandlike structure and small, separated PS phases as protrusions over the macroscopically flat surface. The microphase structure of the PS‐b‐PDMS copolymer thin films was also strongly influenced by the different substrates; for an asymmetric block copolymer thin film, the PDMS and PS phases on a silicon substrate presented a lamellar structure parallel to the surface at intervals. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1010–1018, 2007     

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 of double‐hydrophilic poly(methylacrylic acid)–poly(ethylene glycol)–poly(methylacrylic acid) triblock copolymers and their micelle formation

The aim of the work reported was to synthesize a series of double‐hydrophilic poly(methacrylic acid)‐block‐poly(ethylene glycol)‐block‐poly(methacrylic acid) (PMAA‐b‐PEG‐b‐PMAA) triblock copolymers and to study their self‐assembly behavior. These copolymeric self‐assembly systems are expected to be potential candidates for applications as carriers of hydrophilic drugs. Bromo‐terminated difunctional PEG macroinitiators were used to synthesize well‐defined triblock copolymers of poly(tert‐butyl methacrylate)‐block‐poly(ethylene glycol)‐block‐poly(tert‐butyl methacrylate) via reversible‐deactivation radical polymerization. After the removal of the tert‐butyl group by hydrolysis, double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers were obtained. pH‐sensitive spherical micelles with a core–corona structure were fabricated by self‐assembly of the double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers at lower solution pH. Transmission electron microscopy and laser light scattering studies showed the micelles were of nanometric scale with narrow size distribution. Solution pH and micelle concentration strongly influenced the hydrodynamic radius of the spherical micelles (48–310 nm). A possible reason for the formation of the micelles is proposed. Copyright © 2010 Society of Chemical Industry     

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     

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     

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     

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     

Block copolymers derived from azobiscyanopentanoic acid. XI. Properties of silicone–PMMA block copolymers prepared via polysiloxane(azobiscyanopentanamide)s

Mechanical, thermal, and surface properties of poly(dimethylsiloxane)–poly(methyl methacrylate) block copolymers (PDMS-b-PMMA) prepared by the use of polysiloxane(azobiscyanopentanamide)s were intensively investigated. The mechanical strength of block copolymers was found to decrease with an increase of siloxane contents. Dynamic mechanical analysis (DMA) of block copolymers having long siloxane chain length (SCL) and high siloxane content revealed the existence of two glass transitions attributable to microphase separation of two segments. Differential scanning calorimetry (DSC) also gave some evidence of microphase separation supporting the DMA results. It was observed that the incorporation of PDMS segments in block copolymers improved thermal stability of PMMA, as confirmed by thermogravimetric analysis. Surface analysis of the block copolymers films cast from several solutions indicated surface accumulation of PDMS segments, as revealed by water contact angle and ESCA measurements.     

Influence of semi‐crystalline poly(ε‐caprolactone) and non‐crystalline polylactide blocks on the thermal properties of polydimethylsiloxane‐based block copolymers

Poly(A)‐block‐poly(B), poly(A)‐block‐poly(B)‐block‐poly(A) and B(A)₂ block copolymers were prepared through coordinated anionic ring‐opening polymerization of ε‐caprolactone (CL) and lactic acid (LA) using hydroxy‐terminated polydimethylsiloxane (PDMS) as initiator. A wide range of well‐defined combinations of PDMS‐block‐PCL and PDMS‐block‐PLA diblock copolymers, PCL‐block‐PDMS‐block‐PCL and PLA‐block‐PDMS‐block‐PLA triblock copolymers and star‐PDMS(PCL)₂ copolymers were thus obtained. The number‐average molar masses and the structure of the synthesized block copolymers were identified using various analytical techniques. The thermal properties of these copolymers were established using differential scanning calorimetry. Considering PDMS‐block‐PCL copolymers, the results demonstrate the complex effect of polymer architecture and PCL block length on the ability of the PDMS block to crystallize or not. In the case of diblock copolymers, crystallization of PCL blocks originated from stacking of adjacent chains inducing the extension of the PDMS block that can easily crystallize. In the case of star copolymers, the same tendency as in triblock copolymers is observed, showing a limited crystallization of PDMS when the length of the PCL block increases. In the case of PDMS‐block‐PLA copolymers, melting and crystallization transitions of the PLA block are never observed. Considering the diblock copolymers, PDMS sequences have the ability to crystallize. © 2019 Society of Chemical Industry     

AB‐ and ABC‐type di‐ and triblock copolymers of poly[styrene‐block‐(ε‐caprolactone)] and poly[styrene‐block‐(ε‐caprolactone)‐block‐lactide]: synthesis,characterization and thermal studies

Polystyrene terminated with benzyl alcohol units was employed as a macroinitiator for ring‐opening polymerization of ε‐caprolactone and L ‐lactide to yield AB‐ and ABC‐type block copolymers. Even though there are many reports on the diblock copolymers of poly(styrene‐block‐lactide) and poly(styrene‐block‐lactone), this is the first report on the poly(styrene‐block‐lactone‐block‐lactide) triblock copolymer consisting of two semicrystalline and degradable segments. The triblock copolymers exhibited twin melting behavior in differential scanning calorimetry (DSC) analysis with thermal transitions corresponding to each of the lactone and lactide blocks. The block derived from ε‐caprolactone also showed crystallization transitions upon cooling from the melt. In the DSC analysis, one of the triblock copolymers showed an exothermic transition well above the melting temperature upon cooling. Thermogravimetric analysis of these block copolymers showed a two‐step degradation curve for the diblock copolymer and a three‐step degradation for the triblock copolymer with each of the degradation steps associated with each segment of the block copolymers. The present study shows that it is possible to make pure triblock copolymers with two semicrystalline segments which also consist of degradable blocks. Copyright © 2009 Society of Chemical Industry     

Polymorphism and crystallization in poly(vinylidene fluoride)/ poly(ϵ‐caprolactone)–block–poly(dimethylsiloxane)–block–poly(ϵ‐caprolactone) blends

The miscibility, crystallization kinetics and crystalline morphology of a new system of poly(vinylidene fluoride)/poly(?‐caprolactone)‐block‐poly(dimethylsiloxane)‐block‐poly(?‐caprolactone) (PVDF/PCL‐b‐PDMS‐b‐PCL) triblock copolymer were investigated by a variety of techniques. The miscibility and phase behaviour of PVDF/PCL‐b‐PDMS‐b‐PCL were studied by determination of the melting point temperature, crystallization kinetics and Fourier transform infrared (FTIR) mapping. Chemical imaging was used as a new technique to characterize the interaction of polymer blends in crystalline morphology. The results demonstrate the existence of characteristic peaks of both PVDF and PCL in the chosen crystalline area. The crystalline structures of PVDF were affected by the PCL‐b‐PDMS‐b‐PCL triblock copolymer and facilitate the formation of the β polymorph which was illustrated by FTIR analysis. The β crystal phase fraction increases significantly on increasing the composition of the PCL‐b‐PDMS‐b‐PCL triblock copolymer. In addition, confined crystallization of PCL within PVDF inter‐lamellar and/or inter‐fibrillar regions was confirmed through polarizing optical microscopy, wide‐angle X‐ray diffraction and small‐angle X‐ray scattering analysis. © 2019 Society of Chemical Industry     

Poly(dimethylsiloxane)urethane‐co‐poly(methyl methacrylate) with 2,4‐toluene diisocyanate and m‐xylene diisocyanate. I. Compatibility and impact strength of copolymers

In this study, slightly crosslinked poly(dimethylsiloxane)urethane‐co‐poly(methyl methacrylate) (PDMS urethane‐co‐PMMA) graft copolymers based on two diisocyanates, 2,4‐toluene diisocyanate (2,4‐TDI) and m‐xylene diisocyanate (m‐XDI), were successfully synthesized. Glass‐transition behaviors of the copolymers were investigated. Results confirm that PDMS–urethane and PMMA are miscible in the 2,4‐TDI system, but are only partially miscible in the m‐XDI system. The methylene groups adjoining the isocyanate in the m‐XDI system show increased phase‐separation behavior over the 2,4‐TDI system, in which the benzene ring adjoins the isocyanate. The functional group of PDMS–urethane improves the impact strength of the copolymers. The toughness depends on the compatibility of PDMS–urethane and PMMA segments in the copolymers. In the m‐XDI system, the impact strength of the copolymer containing 3.75 phr macromonomer achieves a maximum value (from 13.02 to 22.21 J/m). The fracture behavior and impact strength of the copolymers in the 2,4‐TDI system are similar to that of PMMA homopolymer, although they are independent of the macromonomer content in the copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1875–1885, 2002     

Synthesis,photophysical properties and microphase separation of all‐conjugated diblock copolymers with hydrophilic side chains

A series of new all‐conjugated diblock copolymers, poly(2,5‐dioctyloxy‐p‐phenylene)‐block‐poly(3‐methoxyethoxyethoxy‐methylthiophene) (PPP‐b‐P3MEEMT), with hydrophilic side‐chains have been synthesized by quasi‐living Grignard metathesis polymerization. The narrow polydispersity indices of the block copolymers are in the range 1.32–1.40. The block ratios in the obtained diblock copolymers can be well defined by the feed ratios of the monomers. Photoluminescence results reveal that resonance energy transfer occurs from the PPP block to the P3MEEMT block in dilute solution. Differential scanning calorimetry shows that both PPP and P3MEEMT blocks in the copolymers produce crystalline regions and lead to microphase separation as indicated by two endothermal transitions, corresponding to the melting peaks of the PPP and P3MEEMT blocks, respectively. The formations of microphase‐separated nanostructures in annealed copolymer films are also observed using transmission electron microscopy. © 2012 Society of Chemical Industry