Morphology of polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) composite particles

Polystyrene/polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) (PS/PS-b-PMMA/PMMA) composite particles were prepared by releasing toluene from PS/PS-b-PMMA/PMMA/toluene droplets dispersed in a sodium dodecyl sulfate aqueous solution. The morphology of the composite particles was affected by release rate of toluene, the molecular weight of PS-b-PMMA, droplet size, and polymer composition. ‘Onion-like’ multilayered composite particles were prepared from toluene droplets of PS-b-PMMA and of PS/PS-b-PMMA/PMMA, in which the weights of PS and PMMA were the same. The layer thicknesses of the latter multilayered composite particles increased with an increase in the amount of the homopolymers. PS-b-PMMA/PS composite particles had a sea-islands structure, in which PMMA domains were dispersed in a PS matrix. On the other hand, PS-b-PMMA/PMMA composite particles had a cylinder-like structure consisting of a PMMA matrix and PS domains.     

Solvent-induced microdomain orientation in polystyrene-b-poly(l-lactide) diblock copolymer thin films for nanopatterning

A series of degradable block copolymers, polystyrene-b-poly(l-lactide) (PS-PLLA), with PLLA hexagonal cylinder (HC) morphology has been synthesized in this study. Well-oriented, perpendicular PLLA cylinders of PS-PLLA thin films were efficiently achieved by spin coating using appropriate solvents regardless of the use of substrates. After hydrolysis of PLLA, well-oriented HC nanochannel arrays over large area in addition to uniform surface with controlled thickness and domain size were obtained; providing a simple and efficient path to prepare nanopatterned templates for applications. The induced orientation of PS-PLLA microdomains was strongly dependent upon the evaporation rate of solvent and its solubility between constituted blocks. The origins for the formed perpendicular HC morphology were systematically studied. The primary concern of controlled morphology for nanopatterning is to develop ordered microphase-separated morphology by considering the time scale for segregation, namely segregation strength during solvent evaporation. The induced orientation is attributed to the permeation discrepancy between phase-separated microdomains. The perpendicular morphology is initiated from the air surface, and formed in order to create an optimized condition (i.e. the fastest path) for solvent evaporation whereas parallel morphology may impede the evaporation of solvent molecules. Following the nucleation of microphase separation, the perpendicular morphology can be kinetically induced by solvent evaporation.     

Induction of chirality into a fully sulfonated poly(methoxyaniline) via acid-base interactions with chiral amines

A wide range of chiral amines and amino alcohols associate with poly(2-methoxyaniline-5-sulfonic acid) (PMAS) in aqueous solution, from which optically active PMAS·(amine) films can be cast. The chiral induction is believed to be initiated by acid-base interactions with “free” sulfonic acid groups on the PMAS chains. Chiral amine:PMAS dimer molar ratios as low as 1:4 give PMAS·(amine) films with similar optical activity to those cast from 1:1 molar mixtures, indicating that only one in four of the “free” sulfonate groups on the PMAS chains need to be electrostatically bound by chiral ammonium ions to achieve optimal chiral induction. Circular dichroism studies show that the enantiomeric amines (R)-(+)- and (S)-(−)-1-phenylethylamine induce the opposite helical hands for the supermolecular assemblies of PMAS chains. However, there is no clear correlation between the sign of the CD signals for the PMAS·(amine) films and the configuration of structurally diverse amines.     

Polymorphism of syndiotactic poly(p-fluoro-styrene)

Syndiotactic poly(p-fluoro-styrene) (s-PPFS) has been prepared with a polymerization procedure which allows reaching high average molecular masses and satisfactory yields. The polymorphic behavior of the polymer has been mainly studied by X-ray diffraction, calorimetric and infrared analyses. The main crystalline phase of s-PPFS, obtained by melt processing or cold-crystallization, exhibits trans-planar chains, is orthorhombic (a = 9.5 Å, b = 28.7 Å, c = 5.1 Å) and melts at nearly 320 °C. The X-ray analysis shows a strict analogy of this orthorhombic phase with the β phase of s-PS, also as for the occurrence of two limit ordered (β″) and disordered (β′) modifications, which differ for the intensity of reflections characterized by h + k = 2n + 1. A metastable crystalline phase, also exhibiting trans-planar chains, has been observed for as-polymerized samples as well as for amorphous samples crystallized by sorption of toluene or 1,4-difluoro-benzene. Mainly on the basis of solvent sorption and desorption experiments, it is suggested that this metastable phase is a co-crystalline phase with the low-molecular-mass guest molecules.     

Purple red and luminescent polyiminoarylenes containing the 1,4-diketo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP) chromophore

New DPP-containing polyiminoarylenes were prepared from 1,4-diketo-2,5-dihexyl-3,6-di(4′-bromophenyl)pyrrolo[3,4-c]pyrrole and various arylamine derivatives using palladium-catalyzed amination reactions. The arylamine comonomers were aniline (ANI), t-butylaniline (TBA), 2-aminoanthracene (AAN), 1-aminopyrene (APY) and N,N′-diphenyl-p-phenylenediamine (PDA). Purple red polymers with good solubility in common organic solvents and molecular weights between 4.4 and 35.8 kDa were obtained. Polymer solutions were readily fluorescent with quantum yields between 19 and 62%, while solution-cast films only showed a weak fluorescence. All polymers exhibit low band gaps of approximately 1.9 eV. Cyclovoltammetric studies indicate quasireversible oxidation for polymers with TBA, APY and PDA as comonomer units, and quasireversible reduction for the polymer with AAN comonomer unit. Polymers with APY and PDA comonomer units are electrochromic and can be switched between red in the neutral and greenish grey in the oxidized state.     

Double-responsive core-shell-corona micelles from self-assembly of diblock copolymer of poly(t-butyl acrylate-co-acrylic acid)-b-poly(N-isopropylacrylamide)

Self-assembly of poly(t-butyl acrylate-co-acrylic acid)-b-poly(N-isopropylacrylamide) [P(tBA-co-AA)-b-PNIPAM], which was obtained from part hydrolysis of PtBA-b-PNIPAM synthesized by sequential atom transfer radical polymerization (ATRP) was studied. Thermo- and pH-responsive core-shell-corona (CSC) micelles with different structures were formed from (PtBA-co-PAA)-b-PNIPAM in aqueous solution. At pH 5.8 and 25 °C, the block copolymer self-assembled into spherical core-shell micelles with hydrophobic PtBA segments as the core, hydrophilic PAA/PNIPAM segments as the mixed shell. Increasing temperatures, core-shell micelles converted into CSC micelles with PtBA as the core, collapsed PNIPAM as the shell and soluble PAA as the corona. Moreover, decreasing pH at 25 °C, PAA chains collapsed onto the core resulting in CSC micelles with PtBA as the core, PAA as the shell and PNIPAM as the corona.     

Comparison of morphologies and mechanical properties of crosslinked epoxies modified by polystyrene and poly(methyl methacrylate)) or by the corresponding block copolymer polystyrene-b-poly(methyl methacrylate)

Polystyrene (PS, M_n=28,400, PI=1.07), poly(methyl methacrylate) (PMMA, M_n=88,600, PI=1.03), and PS (50,000)-b-PMMA (54,000) (PI=1.04), were used as modifiers of an epoxy formulation based on diglycidyl ether of bisphenol A (DGEBA) and m-xylylene diamine (MXDA). Both PS and PMMA were initially miscible in the stoichiometric mixture of DGEBA and MXDA at 80 °C, but were phase separated in the course of polymerization. Solutions containing 5 wt% of each one of both linear polymers exhibited a double phase separation. A PS-rich phase was segregated at a conversion close to 0.02 and a PMMA rich phase was phase separated at a conversion close to 0.2. Final morphologies, observed by scanning electron microscopy (SEM), consisted on a separate dispersion of PS and PMMA domains. A completely different morphology was observed when employing 10 wt% of PS-b-PMMA as modifier. PS blocks with M_n=50,000 were not soluble in the initial formulation. However, they were dispersed as micelles stabilized by the miscible PMMA blocks, leading to a transparent solution up to the conversion where PMMA blocks began to phase separate. A coalescence of the micellar structure into a continuous thermoplastic phase percolating the epoxy matrix was observed. The elastic modulus and yield stress of the cured blend modified by both PS and PMMA were 2.64 GPa and 97.2 MPa, respectively. For the blend modified by an equivalent amount of block copolymer these values were reduced to 2.14 GPa and 90.0 MPa. Therefore, using a block copolymer instead of the mixture of individual homopolymers and selecting an appropriate epoxy-amine formulation to provoke phase separation of the miscible block well before gelation, enables to transform a micellar structure into a bicontinuous thermoplastic/thermoset structure that exhibits the desired decrease in yield stress necessary for toughening purposes.     

Effect of [Mn(acac)3] and its combination with 2,2′-bipyridine on the autoxidation and oligomerisation of ethyl linoleate

In this study we investigated the autoxidation and oligomerisation of ethyl linoleate (EL) catalysed by [Mn(III)(acac)₃] (acac=2,4-pentanedionate) and its combination with 2,2-bipyridine (bpy), in comparison with the EL catalysed by Co(II) 2-ethylhexanoate (Co-EH). EL is a model compound for the alkyd resin in alkyd paints, Co-EH is a common drying catalyst for alkyd paints, and [Mn(acac)₃] and the [Mn(acac)₃]/bpy combination are potential new drying catalysts. The autoxidation of EL was studied through time-resolved Raman spectroscopy, oxygen uptake measurements, and peroxide amount determination. To follow the oligomerisation of EL in time, size exclusion chromatography was used. Head-space GC-MS measurements were performed to determine the amounts of hexanal and pentanal that were formed as volatile byproducts during the autoxidation of EL. The autoxidation rates of EL in the presence of Co-EH and [Mn(acac)₃]/bpy were found to be similar, while the rate in the presence of [Mn(acac)₃] was slower. The extent of EL oligomerisation was much higher for [Mn(acac)₃] compared to the other catalysts. Different mechanisms are proposed for the mode of action for each of the catalysts: Co-EH is primarily a hydroperoxide decomposition catalyst, as is [Mn(acac)₃], only less active. The [Mn(acac)₃]/bpy combination probably forms the very reactive complexes [Mn(III)(acac)₂(bpy)]⁺ and [Mn(II)(acac)₂(bpy)], which are responsible for a very high autoxidation rate, but also for significant degradation of the formed EL oligomers via β-scission reactions due to the promotion of alkoxy radical formation.     

Synthesis and characterisation of hydroxyl end-capped telechelic polymers with poly(methyl methacrylate)-block-poly(n-butyl acrylate) backbones via atom transfer radical polymerisation

Hydroxyl end-capped telechelic polymers with poly(methyl methacrylate)-block-poly(n-butyl acrylate) (PMMA-b-PBA) backbones have been prepared via atom transfer radical polymerisation (ATRP) together with a nucleophilic substitution reaction. A hydroxyl-functionalised PMMA macroinitiator (HO-PMMA-Br) was prepared via ATRP at the optimised reaction temperature (60 °C) using 2-hydroxyethyl 2-bromoisobutyrate as the initiator. The high functionality of the bromo end group in the macroinitiator was confirmed by both ¹H NMR technique and a chain-extension reaction. Electrospray ionisation mass spectrometer proved to be a valuable tool for characterising PMMAs with a bromo end group (PMMA-Br), which provided signals corresponding to the intact polymers although multiply charged polymer chains were observed. The well-defined block copolymers HO-PMMA-b-PBA-Br were obtained by the ATRP of n-butyl acrylate using HO-PMMA-Br as a macroinitiator in a one-pot reaction at 100 °C. The kinetics as well as the dependence of the M_n,SEC and PDIs of the obtained block copolymers on the conversions of n-butyl acrylate in the chain-extension reaction suggested negligible radical termination during the reaction, demonstrating that the well-defined HO-PMMA-b-PBA-Br with a high functionality of bromo end group were obtained. The nucleophilic substitution reaction of a monohydroxyl-functionalised block copolymer HO-PMMA-b-PBA-Br with 5-amino-1-pentanol in dimethyl sulfoxide at room temperature was verified with ¹H and ¹³C NMR techniques, which resulted in a series of telechelic polymers HO-PMMA-b-PBA-OH with a functionality of hydroxyl groups up to 1.7 according to the gradient polymer elution chromatography.     

Nanostructured thermosets from epoxy and poly(2,2,2-trifluoroethyl acrylate)-block-poly(glycidyl methacrylate) diblock copolymer: Demixing of reactive blocks and thermomechanical properties

Poly(2,2,2-trifluoroethyl acrylate)-block-poly(glycidyl methacrylate) (PTFEA-b-PGMA) diblock copolymer was synthesized via sequential reversible addition-fragmentation chain transfer (RAFT) polymerization. The reactive diblock copolymer was incorporated into epoxy to obtain the nanostructured thermosets. The morphology of the thermosets was investigated by means of atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS). It is identified that the demixing of the reactive subchain (viz. PGMA) out of epoxy matrix occurred in the process of curing reaction, which exerted a profound impact on the glass transition temperatures of the nanostructured thermosets. The static contact angle measurements showed that the nanostructured thermosets displayed a significant enhancement in surface hydrophobicity as well as a reduction in surface free energy. The improvement in surface properties was attributed to the enrichment of the fluorine-containing block (i.e., PTFEA) of amphiphilic diblock copolymer on the surface of the thermosets, which was further evidenced by surface atomic force microscopy (AFM). The measurement of critical stress intensity factor (K_1C) showed that the fracture toughness of the materials was significantly enhanced by the inclusion of a small amount of PTFEA-b-PGMA diblock copolymer.     

Nanopatterns of poly(styrene-block-butyl acrylate) block copolymer brushes on the surfaces of exfoliated and intercalated clay layers

We report a study of poly(styrene-block-butyl acrylate) (PSBA) block copolymer brushes on the surfaces of intercalated and exfoliated silicate (clay) layers. The PSBA/clay nanocomposite was synthesized by in situ atom transfer radical polymerization (ATRP) from initiator moieties immobilized within the silicate galleries of the clay particles. Transmission electron microscopy (TEM) analysis showed the existence of both intercalated and exfoliated structures in the nanocomposite. Block copolymer brushes on the surface of exfoliated or intercalated clay layers were found to create nanopatterns after treatment in different solvents. For the block copolymer brushes after treatment in THF, uniform collapsed brush layers are observed. After treatment in acetone, a selective solvent for PBA, wormlike surface aggregates are observed. After treatment in methanol, a precipitant for both of the blocks, micelles as well as wormlike aggregates can be observed. Furthermore, the polymer brushes tend to aggregate together and change their nanopatterns at an elevated temperature.     

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.     

Influence of a hydrogen-bonding co-monomer on polymer diffusion in poly(butyl acrylate-co-methyl methacrylate) latex films

Small amounts of hydrogen-bonding comonomers such as N-(2-methacryloxyethyl)ethylene urea (MEEU) are often included in latex particle synthesis to promote adhesion of latex films to metals and old surfaces. Little is known about how these monomers affect the latex film formation process. Here we examine the influence of 1-7 wt.% MEEU on butyl acrylate-methyl methacrylate copolymer latex films using fluorescence resonance energy transfer (FRET) measurements, in conjunction with donor- and acceptor-labeled latex particles, to study the rates of polymer diffusion in these films. The presence of MEEU in the copolymer leads to small increases in the polymer glass transition temperature (Tg). It also tends to retard the rate of polymer diffusion. This effect, however, is very sensitive to the humidity of the surrounding atmosphere. It appears that moisture taken up in the film minimizes the influence of MEEU groups on the rate of polymer diffusion.     

Dispersion polymerization of 2-hydroxyethyl methacrylate stabilized by a hydrophilic/CO2-philic poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) (PEO-b-PFDA) diblock copolymer in supercritical carbon dioxide

Dispersion polymerization of 2-hydroxyethyl methacrylate (HEMA) has been successfully performed in supercritical carbon dioxide at P=370 bar and T=65 °C with azobis(isobutyronitrile) as initiator and a hydrophilic/CO₂-philic poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) (PEO-b-PFDA) block copolymer as steric stabilizer. The PEO-b-PFDA (2K/21K) block copolymer was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Spherical particles of poly(HEMA) were obtained in the range of 200-400 nm diameter size with a narrow particle size distribution (D_w/D_n<1.1). The effect of the stabilizer concentration on the dispersion polymerization was investigated from 20 w/w% down to 3.5 w/w% versus HEMA. Precipitation polymerization in the absence of stabilizer lead to the formation of large aggregates of partially coalesced particles whereas discrete spherical particles of poly(HEMA) were obtained by dispersion polymerization even at low concentration of PEO-b-PFDA (3.5 w/w% versus HEMA).     

Influence of diblock copolymer on the morphology and properties of polystyrene/poly(dimethylsiloxane) blends

Blends of polystyrene (PS) and poly(dimethylsiloxane) (PDMS), with and without diblock copolymers (PS‐b‐PDMS), were prepared by melt mixing. The melt rheology behavior of the blends was studied with a capillary rheometer. The morphology of the blends was examined with scanning electron microscopy. The miscibility of the blends was studied with differential scanning calorimetry. The morphology of PS/PDMS blends was modified by the addition of PS‐b‐PDMS copolymers and investigated as a function of the molar mass of the diblock copolymers, viscosity ratios and the processing conditions. As investigated, the observed morphology of the melt‐blended PS/PDMS pair unambiguously supported the interfacial activity of the diblock copolymers. When a few percent of the diblock copolymers blended together with the PS and PDMS homopolymers, the phase size was reduced and the phase dispersion was firmly stabilized against coalescence. The compatibilizing efficiency of the copolymers was strongly dependent on its molar mass. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2747–2757, 2004     

Polyurethane-poly(methyl methacrylate) interpenetrating polymer networks: 2. Influence of compositional parameters on the synthesis; physical properties

According to a previously established general preparation scheme, polyurethane-poly(methyl methacrylate) interpenetrating polymer networks with various compositions and crosslinker contents were prepared. The influence of kinetics of the individual networks on the resulting composites was also examined. Only about 5% soluble species were extractible, thus showing a satisfactory completion of the different reaction systems. Physical properties such as transparency, refractive index, density and swelling behaviour were determined.     

Ion-dipole interactions in the dispersion of organoclay nanocomposites based on polystyrene-block-poly(2-vinylpyridine) copolymer

The dispersion characteristics of organoclay nanocomposites based on polystyrene-block-poly(2-vinylpyridine) (S2VP diblock) copolymer were investigated using transmission electron microscopy (TEM), X-ray diffraction (XRD), and solid-state nuclear magnetic resonance (NMR) spectroscopy. For the investigation, S2VP diblock copolymers having three different compositions were synthesized via sequential anionic polymerization. Each S2VP diblock copolymer was used to prepare nanocomposites by solution blending with natural clay (montmorillonite, MMT) or commercial organoclays (Cloisite 30B, Cloisite 10A, Cloisite 15A, and Cloisite 25A from Southern Clay Products). All four organoclays employed were treated with a surfactant having quaternary ammonium salt with N⁺ ion. It was found, via TEM and XRD, that the nanocomposites with MMT show very poor dispersion characteristics regardless of block copolymer composition. However, the block copolymer composition was found to have a profound influence on the dispersion characteristics of the nanocomposites with an organoclay. Specifically, the nanocomposites based on S2VP-5 having 5 wt% poly(2-vinylpyridine) (P2VP) block gave rise to a very high degree of dispersion, irrespective of the chemical structure of the surfactant residing at the surface of the organoclay employed, whereas the dispersion characteristics of the nanocomposites became progressively poorer as the amount of P2VP block in an S2VP diblock copolymer increased from 5 to 25 wt% and to 56 wt%. The observed dispersion characteristics were explained by hypothesizing the presence of ion-dipole interactions between the positively charged N⁺ ions in the surfactant residing at the surface of the organoclay nanoparticles and the dipoles in the P2VP block of S2VP diblock copolymers. The validity of this hypothesis was confirmed using solid-state NMR spectroscopy, by determining the dependence of the composition of S2VP diblock copolymer on the extent of ion-dipole interactions and thus on the dispersion characteristics of the nanocomposites prepared.     

Dissipative particle dynamics study on the multicompartment micelles self-assembled from the mixture of diblock copolymer poly(ethyl ethylene)-block-poly(ethylene oxide) and homopolymer poly(propylene oxide) in aqueous solution

Dissipative particle dynamics (DPD) method is applied to model the self-assembly of diblock copolymer poly(ethyl ethylene)-block-poly(ethylene oxide) (PEE-b-PEO) and homopolymer poly(propylene oxide) (PPO) in aqueous solution. In this study, several segments are coarse-grained into a single simulation bead based on the experimental density. For the self-assembly of pure diblock copolymer PEE-b-PEO in dilute solution, the DPD simulation results are in good agreement with experimental data of micelle morphologies and sizes. The chain lengths of the block copolymers and the volume ratios between PPO and PEE-b-PEO are varied to find the conditions of forming multicompartment micelles. The micelles with core-shell-corona structure and the micelles with two compartments are both formed from the mixture of PEE-b-PEO and PPO in aqueous solution.     

Influence of the solvent and the end groups on the morphology of cross-linked amphiphilic poly(1,2-butadiene)-b-poly(ethylene oxide) nanoparticles

The phase diagrams of nanoparticles based on self-assembled amphiphilic poly(1,2-butadiene)-b-poly(ethylene oxide) diblock copolymers (PB-b-PEO) and subsequent intra-micellar cross-linking in methanol and water show that the obtained morphology of the nanoparticles depends on: (i) the block ratio; (ii) the block length; (iii) the solvent; and (iv) the PEO-sided end group. Depending on these parameters, spherical, cylindrical and vesicle-like nanoparticles are synthesized. The PEO-sided end group is found to have an influence on the morphology of the nanoparticles and in addition, it has an impact on the characteristic dimension of the polymeric nanoparticles.