Synthesis of poly(ethylene oxide)-block-poly(methyl methacrylate)-block-polystyrene triblock copolymers by two-step atom transfer radical polymerization

The synthesis of ABC triblock copolymer poly(ethylene oxide)-block-poly(methyl methacrylate)-block-polystyrene (PEO-b-PMMA-b-PS) via atom transfer radical polymerization (ATRP) is reported. First, a PEO-Br macroinitiator was synthesized by esterification of PEO with 2-bromoisobutyryl bromide, which was subsequently used in the preparation of halo-terminated poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) diblock copolymers under ATRP conditions. Then PEO-b-PMMA-b-PS triblock copolymer was synthesized by ATRP of styrene using PEO-b-PMMA as a macroinitiator. The structures and molecular characteristics of the PEO-b-PMMA-b-PS triblock copolymers were studied by FT-IR, GPC and ¹H NMR.     

Epoxy resin containing poly(ethylene oxide)-block-poly(?-caprolactone) diblock copolymer: Effect of curing agents on nanostructures

An amphiphilic diblock copolymer, poly(ethylene oxide)-block-poly(?-caprolactone) (PEO-b-PCL) was synthesized via the ring-opening polymerization of ?-caprolactone in the presence of a hydroxyl-terminated poly(ethylene oxide) monomethyl ether. The diblock copolymer was incorporated into epoxy thermosets. It is found that the formation of nanostructures of thermosetting blends is quite dependent on the uses of aromatic amine hardeners. For 4,4′-methylenebis(2-chloroaniline) (MOCA)-cured thermosetting system, the homogeneous morphology was obtained at the compositions investigated. Nonetheless, the nanostructured thermosets were obtained when the blends were cured with 4,4′-diaminodiphenylsulfone (DDS). The differential scanning calorimetry (DSC) showed that the nanostructured thermosets did not displayed any crystallinity although the subchains of the diblock copolymer are crystalline. The nanostructures were evidenced by means of atomic force microscopy (AFM), small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The dependence of morphological structures on the types of aromatic amines for epoxy and PEO-b-PCL thermosetting blends were interpreted on the basis of the difference in hydrogen bonding interactions resulting from the structure of curing agents. Considering the complete miscibility of the subchains (viz. PEO and PCL) with the precursors of epoxy resin before curing, it is judged that the formation of the nanostructures in the thermosets follows the mechanism of reaction-induced microphase separation, which is in marked contrast to the mechanism of self-assembly, i.e., micelle structures of block copolymers are formed prior to curing, followed by fixing these nanostructures via curing.     

Formation of nanostructures in thermosets containing block copolymers: From self-assembly to reaction-induced microphase separation mechanism

In this work, we investigated the effect of formation mechanisms of nanophases on the morphologies and thermomechanical properties of the nanostructured thermosets containing block copolymers. Toward this end, the nanostructured thermosets involving epoxy and block copolymers were prepared via self-assembly and reaction-induced microphase separation approaches, respectively. Two structurally similar triblock copolymers, poly(ε-caprolactone)-block-poly(butadiene-co-styrene)-block-poly(ε-caprolactone) (PCL-b-PBS-b-PCL) and poly(ε-caprolactone)-block-poly(ethylene-co-ethylethylene-co-styrene)-block-poly(ε-caprolactone) (PCL-b-PEEES-b-PCL) were synthesized via the ring-opening polymerization of ε-caprolactone (CL) with α,ω-dihydroxyl-terminated poly(butadiene-co-styrene) (HO-PBS-OH) and α,ω-dihydroxyl-terminated poly(ethylene-co-ethylethylene-co-styrene) (i.e., HO-PEEES-OH) as the macromolecular initiators, respectively; the latter was obtained via the hydrogenation reduction of the former. Both the triblock copolymers had the same architecture, the identical composition and close molecular weights. In spite of the structural resemblance of both the triblock copolymers, the formation mechanisms of the nanophases in the thermosets were quite different. It was found that the formation of nanophases in the thermosets containing PCL-b-PBS-b-PCL followed a reaction-induced microphase separation mechanism whereas that in the thermosets containing PCL-b-PEEES-b-PCL was in a self-assembly manner. The different formation mechanisms of nanophases resulted in the quite different morphologies, glass transition temperatures (T_g's) and fracture toughness of the nanostructured thermosets.     

A new approach in the study of tethered diblock copolymer surface morphology and its tethering density dependence

A poly(l-lactic acid)-block-polystyrene-block-poly(methyl methacrylate) (PLLA-b-PS-b-PMMA) triblock copolymer was synthesized with a crystalline PLLA end block. Single crystals of this triblock copolymer grown in dilute solution could generate uniformly tethered diblock copolymer brushes, PS-b-PMMA, on the PLLA single crystal substrate. The diblock copolymer brushes exhibited responsive, characteristic surface structures after solvent treatment depending upon the quality of the solvent in relation to each block. The chemical compositions of these surface structures were detected via the surface enhanced Raman scattering technique. Using atomic force microscopy, the physical morphologies of these surface structures were identified as micelles in cyclohexane and “onion”-like morphologies in 2-methoxyethanol, especially when the PS-b-PMMA tethered chains were at low tethering density.     

Reaction-induced microphase separation in polybenzoxazine thermosets containing poly(N-vinyl pyrrolidone)-block-polystyrene diblock copolymer

Poly(N-vinyl pyrrolidone)-block-polystyrene diblock copolymer (PVPy-b-PS) was synthesized via sequential reversible radical-fragmentation transfer polymerization with S-1-phenylethyl O-ethylxanthate as a chain transfer agent. The block copolymer was incorporated into polybenzoxazine to access the nanostructures in the thermosets. The nanostructures in the thermosets were investigated by means of transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). It was found that disordered and/or ordered PS nanophases were formed in the PBa thermosets. It is judged that the formation of nanophases followed the mechanism of reaction-induced microphase separation in terms of the miscibility of the subchains of the diblock copolymer (viz. PVPy and PS) with polybenzoxazine after and before curing reaction.     

Thermosets with core-shell nanodomain by incorporation of core crosslinked star polymer into epoxy resin

Core crosslinked star (CCS) polymers, which have crosslinked poly (divinyl benzene-co-styrene) [P(DVB-St)] core and multiple arms of polystyrene-b-poly(ethylene oxide) diblock copolymer (PEO-b-PS) [denoted as PEO-b-PS/P(DVB-St) CCS], were synthesized via atom transfer radical polymerization(ATRP). PEO-b-PS/P(DVB-St) CCS polymer was spherical with average diameters of scores of nanometers from transmission electron microscopy (TEM) and dynamic light scattering (DLS), and blended with diglycidyl ether of bisphenol (DGEBA) and 4,4′-diamino diphenyl methane (DDM) in tetrahydrofuran (THF). With 5 or 10 wt% PEO-b-PS/P(DVB-St) CCS polymer, spherical core-shell nanodomains with average diameters of 29 or 32 nm were observed from atomic force microscopy (AFM), which were randomly distributed in the resultant thermosets. Considering the difference in miscibility of the epoxy with P(DVB-St) and PEO-b-PS after and before curing reaction, a reaction-induced microphase separation (RIMPS) mechanism was proposed to account for the formation of the core-shell nanodomains in the thermosets. During curing, the RIMPS of PS subchain occurred but was confined by P(DVB-St) core, resulting in formation of thermoplastic PS shell around the crosslinked core. Such core-shell nanodomain could be easily etched away by THF, whereas the control thermosets containing PEO/P(DVB-St) CCS polymer could not be etched by THF. The glass transition temperatures (T_gs) of the epoxy thermosets containing PEO-b-PS/P(DVB-St) CCS polymer were significantly improved compared with pure epoxy thermosets.     

运用嵌段共聚物在热固性树脂中构建纳米尺度上的微结构(下)

通过嵌段共聚物在环氧树脂中的微相分离能够构建具有不同形貌纳米结构的热固性树脂,从而改善环氧树脂的性能.自组装机理和反应诱致微相分离机理作为环氧树脂中构建纳米结构的机理已得到众多环氧树脂研究工作者的认可,这为进一步于环氧树脂中构建新型的纳米结构提供了有利的支撑.本文针对自组装机理和反应诱致微相分离机理进行了阐述,并对通过...     

运用嵌段共聚物在热固性树脂中构建纳米尺度上的微结构(上)

通过嵌段共聚物在环氧树脂中的微相分离能够构建具有不同形貌纳米结构的热固性树脂,从而改善环氧树脂的性能。自组装机理和反应诱致微相分离机理作为环氧树脂中构建纳米结构的机理已得到众多环氧树脂研究工作者的认可,这为进一步于环氧树脂中构建新型的纳米结构提供了有利的支撑。本文针对自组装机理和反应诱致微相分离机理进行了阐述,并对通过两种机理在环氧树脂中构建纳米结构的研究进展及纳米微相结构对热固性树脂性能的影响做了概述,以期对环氧树脂更为广泛的应用提供一定的帮助。     

Dispersion of polymer-grafted magnetic nanoparticles in homopolymers and block copolymers

The dispersion of magnetic nanoparticles (NPs) in homopolymer poly(methyl methacrylate) (PMMA) and block copolymer poly(styrene-b-methyl methacrylate) (PS-b-PMMA) films is investigated by TEM and AFM. The magnetite (Fe₃O₄) NPs are grafted with PMMA brushes with molecular weights from M = 2.7 to 35.7 kg/mol. Whereas a uniform dispersion of NPs with the longest brush is obtained in a PMMA matrix (P = 37 and 77 kg/mol), NPs with shorter brushes are found to aggregate. This behavior is attributed to wet and dry brush theory, respectively. Upon mixing NPs with the shortest brush in PS-b-PMMA, as-cast and annealed films show a uniform dispersion at 1 wt%. However, at 10 wt%, PS-b-PMMA remains disordered upon annealing and the NPs aggregate into 22 nm domains, which is greater than the domain size of the PMMA lamellae, 18 nm. For the longest brush length, the NPs aggregate into domains that are much larger than the lamellae and are encapsulated by PS-b-PMMA which form an onion-ring morphology. Using a multi-component Flory-Huggins theory, the concentrations at which the NPs are expected to phase separate in solution are calculated and found to be in good agreement with experimental observations of aggregation.     

The effect of reaction-induced micro-phase separation of block copolymer on curing kinetics of epoxy thermosets

The curing kinetics of epoxy system modified with Poly(ε-caprolactone)-block-Polystyrene (PCL-b-PS) diblock copolymer was investigated by differential scanning calorimetry(DSC). PCL-b-PS was synthesized Via the combination of ROP and ATRP, then incorporated into epoxy to access the nanostructured thermosets. The results of TEM, SAXS and DSC demonstrated the occurrence of Reaction-induced Micro-phase Separation. Kinetic studies showed that the PCL-b-PS block copolymer delayed the curing reactions of epoxy system. The occurrence of Reaction-induced Micro-phase Separation had no significant effect on the total heat of reaction ?H and the total activation energy, but resulted in a higher activation energy at the beginning of curing. The increase in activation energy at the initial stage of curing was related to the size and distribution of the dispersed phase. It is expected that the investigation of cure kinetics of EP/PCL-b-PS could provide more theoretical basis for the preparation of block copolymer modified epoxy resin.     

Directed self-assembly of block copolymers by chemical or topographical guiding patterns: Optimizing molecular architecture,thin-film properties,and kinetics

Patterning strategies based on directed self-assembly (DSA) of block copolymers, as one of the most appealing next-generation lithography techniques, have attracted abiding interest. DSA aims at fabricating defect-free geometrically simple patterns on large scales or irregular device-oriented structures. Successful application of DSA requires to control and optimize multiple process parameters related to the bulk morphology of the block copolymer, its interaction with the chemical or topographical guiding pattern, and the kinetics of structure formation. Most studies have focused on validating DSA patterning techniques using PS-b-PMMA block copolymers as a prototypical material. As the development of DSA techniques advances, recent efforts have been devoted to extending the materials selection in order to fabricate more complex geometric patterns or patterns with smaller characteristic dimensions. How to select appropriate polymer materials in a vast parameter space is a critical but also challenging step. In this review, we discuss recent progress in the research of DSA of block copolymers focusing on three aspects: (i) screening the block copolymer materials, (ii) controlling the film properties, and (iii) tailoring the phase separation kinetics.     

Micellar morphologies of self-associated diblock copolymers in acetone solution

We describe the synthesis and solution morphologies of poly(vinyl phenol-b-styrene) (PVPh-b-PS) micelles and the effects that changing the copolymer composition and concentration have on self-assembly structures of PVPh-b-PS in acetone (a good solvent for PVPh). These PVPh-b-PS copolymers aggregated into spherical, rod-like, and vesicular morphologies. The transformations of the PVPh-b-PS block copolymer micelles in acetone depended on a number of parameters, including the relative block lengths, their concentrations, and the degree of self-association through hydrogen bonding of the coronal PVPh chains. We also investigated the morphologies of the micelles formed from acetone solutions of poly(4-tert-butoxystyrene-b-styrene) (PtBOS-b-PS) copolymers having the same degree of polymerization as the precursor of PVPh-b-PS copolymer before hydrolysis reaction. Our results indicate that the micelles formed from PVPh-b-PS copolymers in acetone were more complicated than those prepared from PtBOS-b-PS copolymers in acetone because hydrogen bonding occurs in the micelle corona of the PVPh block. Finally, we also discussed the morphology transition when the self-association hydrogen bonding of PVPh block was destroyed by adding proton acceptor poly(4-vinylpyridine) (P4VP).     

Studies of the properties of a thermosetting epoxy modified with block copolymers

Poly[(n‐butyl acrylate)‐block‐poly(methyl methacrylate)‐co‐(glycidyl methacrylate)] (BMG) diblock copolymers incorporating an epoxy‐reactive functionality in one block have been synthesized and used as modifiers for the model epoxy resin E‐51 cured with 4,4′‐diaminodiphenyl methane (DDM). The properties and morphologies of the modified epoxy thermosets were investigated by dynamic mechanical analysis (DMA), impact testing and scanning electron microscopy (SEM). The results reveal that addition of the block copolymers leaves the glass transition temperatures of the blends relatively unchanged, with small decreases in the storage moduli at room temperature. The toughening effect is dependent on the chemical structures of the block copolymers and an increase in the impact strength by a factor of two was obtained by the addition of ‘relatively symmetrical’ block copolymers. Moreover, the impact test results are consistent with the morphologies of the fracture surfaces as evidenced by SEM. Copyright © 2005 Society of Chemical Industry     

Development of nano-channel single crystals and verification of their structures by small angle X-ray scattering

Nano-channel single crystals were developed via consecutive growth of various polymer single-crystal channels comprising homo and block copolymers by self-seeding method. Poly(ethylene glycol)-b-polystyrene (PEG-b-PS) and poly(ethylene glycol)-b-poly(methyl methacrylate) (PEG-b-PMMA) block copolymers were synthesized by atom transfer radical polymerization. Self-seeding temperature, concentration, and crystallization time affected the width of the channels. This might provide a new way to investigate directional absorption, diffusion, and immobilization of biomacromolecules on the surface. The crystalline blocks of PEG-b-PS and PEG-b-PMMA diblock copolymers were similar, therefore, the continuity of channel-wire growth was guaranteed. Development of complete square channels next to the channels covered with high molecular weight brushes was infeasible. It was ascribed to a higher hindrance of primarily existing tethered chains on the single-crystal channel. Finally, the consecutive channel-wire single crystals were compared with single-step-grown pyramidal and conic structures. These multilayer crystals grew spirally and formed non-flat channels. The structure and morphology of different crystalline channels were detected by atomic force microscopy (AFM) and small angle X-ray scattering (SAXS). In this work, for the first time, the SAXS data of channel-wire single crystals were reported and they were compared by non-flat channel-like crystals. A profound investigation of PEG-b-PS, PEG-b-PMMA copolymers and PEG homopolymer channel-wire single crystals by SAXS and their comparison with AFM data was a novel work in the field of single-crystal engineering.     

Synthesis and self-assembly behaviors of three-armed amphiphilic block copolymers via RAFT polymerization

The novel trifunctional reversible addition-fragmentation chain transfer (RAFT) agent, tris(1-phenylethyl) 1,3,5-triazine-2,4,6-triyl trithiocarbonate (TTA), was synthesized and used to prepare the three-armed polystyrene (PS₃) via RAFT polymerization of styrene (St) in bulk with thermal initiation. The polymerization kinetic plot was first order and the molecular weights of polymers increased with the monomer conversions with narrow molecular weight distributions (M_w/M_n ≤ 1.23). The number of arms of the star PS was analyzed by gel permeation chromatography (GPC), ultraviolet visible (UV-vis) and fluorescence spectra. Furthermore, poly(styrene-b-N-isopropylacrylamide)₃ (PS-b-PNIPAAM)₃, the three-armed amphiphilic thermosensitive block copolymer, with controlled molecular weight and well-defined structure was also successfully prepared via RAFT chain extension method using the three-armed PS obtained as the macro-RAFT agent and N-isopropylacrylamide as the second monomer. The copolymers obtained were characterized by GPC and ¹H nuclear magnetic resonance (NMR) spectra. The self-assembly behaviors of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ in mixed solution (DMF/CH₃OH) were also investigated by high performance particle sizer (HPPS) and transmission electron microscopy (TEM). Interestingly, the lower critical solution temperature (LCST) of aqueous solutions of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ decreased with the increase of relative length of PS in the block copolymers.     

Non-reactive and reactive block copolymers for toughening of UV-cured epoxy coating

Reactive and non-reactive diblock copolymers based on polyethylene oxide (PEO) and a poly(glycidyl methacrylate) (PGMA, reactive) or polystyrene (non-reactive) block, respectively, are prepared via ATRP and those are incorporated into a cycloaliphatic epoxy matrix. Crosslinking of the matrix is then performed by cationic UV curing, producing modified thermosets. ¹H NMR and SEC measurements are carried out and used to analyze the composition, the molar mass and dispersity of the prepared block copolymers. The viscoelastic properties and morphology of the modified epoxy are determined using DMTA and FESEM, respectively. The addition of 4 and 8 wt% of the reactive PEO-b-PGMA block copolymer into epoxy resin has only minor effects on the glass transition temperature, T_g. The reactive homopolymer PGMA significantly increases and the non-reactive block copolymer PEO-b-PS slightly decreases the glass transition temperature of the epoxy matrix. The non-reactive block copolymer PEO-b-PS causes a little decrease in T_g values. The measurement of the critical stress factor, K_IC, shows that the fracture toughness of the composite materials is enhanced by inclusion of the non-reactive block copolymer. In contrary, the reactive block copolymer has negative effect on the fracture toughness especially in case of short PEO block. FESEM micrographs studies on the fracture surfaces sustain the microphase separation and the increase in surface roughness in the toughened samples, indicating more energy was dissipated.     

Vesicle formation of polystyrene-block-poly (ethylene oxide) block copolymers induced by supercritical CO2 treatment

A novel route for a preparation of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymer vesicles induced by supercritical carbon dioxide (scCO₂) is demonstrated. When PS-b-PEO block copolymer solutions in tetrahydrofuran (THF) are treated with scCO₂ at 70 °C for different times, PS-b-PEO copolymers first assemble into aggregated spheres; then aggregated spheres change into large compound micelles and finally evolve into vesicles. The possible formation mechanism of the vesicles is discussed.     

Morphology and thermomechanical properties of nanostructured thermosetting blends of epoxy resin and poly(?-caprolactone)-block-polydimethylsiloxane-block-poly(?-caprolactone) triblock copolymer

Poly(?-caprolactone)-block-polydimethylsiloxane-block-poly(?-caprolactone) triblock copolymer (PCL-b-PDMS-b-PCL) was synthesized via the ring-opening polymerization of ?-caprolactone with dihydroxypropyl-terminated PDMS (HTPDMS) as the initiator. The triblock block copolymer was characterized by means of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). The triblock copolymer was incorporated to prepare nanostructured thermosetting blends. The morphology of the epoxy thermosets containing PCL-b-PDMS-b-PCL were investigated by means of atomic force microscopy (AFM), transmission electronic microscopy (TEM) and small-angle X-ray scattering (SAXS). The thermomechanical properties of the nanostructured blends were investigated by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The formation of the nanostructures in the thermosetting composites was judged to follow the self-assembly mechanism in terms of the difference in miscibility of PDMS and PCL subchains with epoxy resin after and before curing reaction.     

Swelling behavior of ordered miktoarm star block copolymer-homopolymer blends

We report the morphological characterization of asymmetric miktoarm star block copolymers of the (PS-b-PI)_nPS type where n=2,3 (denoted 2DB and 3DB miktoarm stars, respectively) and a symmetric super H-shaped block copolymer of the (PS-b-PI)₃PS(PI-b-PS)₃ type (denoted SH) which were synthesized by anionic polymerization. The initial volume fraction of PS (φ_PS) for each copolymer was 0.51-0.56, giving a lamellar morphology. Addition of homopolystyrene (hPS) with a molecular weight lower than the respective PS blocks in the neat materials lead to a transition from the lamellar structure to hexagonally packed cylinders. Addition of low molecular weight homopolyisoprene (hPI) on the other hand, only resulted in swollen lamellae even when the overall composition was highly asymmetric (80/20). Changes in the lamellar spacing as well as in the respective PS and PI layer thickness were measured by SAXS. The transition from lamellae to cylinders with increased PS content occurred without the observation of an intervening cubic morphology for the 2DB and 3DB miktoarm stars. However, blends with 30 and 35% hPS ((φ_PS)_total=0.68-0.70) with the super H-shaped block copolymer lead to the observation of lamellar-catenoid structures.     

Thiol-benzoxazine chemistry as a novel Thiol-X reaction for the synthesis of block copolymers

A novel synthetic procedure is reported for the preparation of block copolymers by means of successive 1,3-benzoxazine-thiol and Husigen type azide-alkyne coupling methodologies in one-pot and sequential synthesis. The applied 1,3-benzoxazine-thiol process based on catalytic opening of the lateral benzoxazine rings by thiols is proposed as a new thiol-X chemistry. Azide functional poly(methyl acrylate) (PMA-N₃), poly(ethylene glycol) (PEG-N₃) and thiol functional polystyrene (PS-SH) were prepared. The obtained PMA-N₃ or PEG-N₃, PS-SH and propargyl benzoxazine as a click-linker were reacted in sequential or one-pot two step manner to yield desired PS-b-PMA and PS-b-PEG block copolymer. The described thiol-benzoxazine chemistry offers a facile and efficient route to exploring the many possibilities in macromolecular synthesis.