Phase behavior of hybrid dendron-linear copolymers and blends with linear homopolymer

The phase behavior of novel hybrid diblock copolymers composed of poly(benzyl ether) dendrons of various generations grafted to deuterated polystyrene tails of varying molecular weights are examined by small angle neutron scattering. Blends of these hybrid copolymers with linear polystyrene of two molecular weights are shown to exhibit dissolution, microphase separation and microphase & mesophase separation depending on the relative molecular weights of the dendrons, tails, and matrix homopolymer. The results suggests that there is a strong entropic penalty against mixing polymers of dendritic architecture with linear chains, and that this driving force can be harnessed to create unique, nanostructured polymer materials. To cite this article: C. R. Chimie 6 (2003).     

Aggregates of amphiphilic fluorinated copolymers and their encapsulating and unloading homopolymer behaviors

Amphiphilic fluorinated block copolymers synthesized via reversible addition‐fragmentation chain transfer polymerization were used for the preparation of aggregates of various morphologies. First, dissolve the copolymer in 2‐butanone; second, add a precipitant solvent, which was the mixture of water and methanol, to induce the aggregation of the hydrophobic fluorinated block. With a hydrophilic tail and a very hydrophobic segment, these copolymers are likely to self‐assemble in solution and form aggregates. Observed by TEM, spheres, rods, and vesicles can be formed by changing the precipitant mixture contents. Besides, these aggregates were found to be able to carry hydrophobic fluorinated homopolymers, and two suggested processes have been proposed to explain their morphology changes from original spheres, rods and vesicles into larger size spheres. Finally, hollow bilayer spheres and tubules can be achieved after extracting homopolymers in the center of the newly formed spheres. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1000–1006, 2008     

Melt crystallized polyamide 6.6 and its copolymers, Part II. Crystallization mechanisms in the homopolymer

The crystallization kinetics of polyamide 66 have been studied using polarized optical microscopy. The growth rate data for positively birefringent spherulites in polyamide 66 show a distinct change of slope, which would be identified as a regime I/II transition based on secondary nucleation theory. However, recent data for the same specimens crystallized isothermally, from small angle X-ray scattering found the lamellar thickness to be constant at approximately 2.0 chemical repeat units, but with an internal crystalline core and a substantial innerlayer. The crystal core increases in size to 2 chemical repeat units with both time and temperature at the expense of the inner layer. This evidence is totally inconsistent with secondary nucleation theory, where a lamellar thickness which varies significantly with supercooling is an integral part of the derivations.A calculation of the dimensions of the critical nucleus is reported here, using surface free energies, which found it to be impossibly large at a value between 14 and 360 stems in size, further suggesting that another crystallization mechanism is operating. Calculations of the surface free energy of the hydrogen-bonded surface suggest that it is the high energy surface, rather than the folded surface, which normally occurs as the high energy surface in polymers. As the high energy surface, the hydrogen-bonded surface would be expected to be the growth face, as occurs in non-polymeric materials. An earlier model of Lovinger, which placed the fold direction into the melt, generating a rough surface, is consistent with these results.It is suggested that crystallization in polyamide 66, if not in all polyamides, occurs through a surface roughening mode of growth. This is a natural consequence of the presence of H-bonding in the direction of growth. In one sense, polyamide 66 is conventional in its growth behavior, relative to non-polymeric materials, as the growth face is the highest energy surface. As such, the lamellar thickness would no longer be a morphological variable related to the supercooling in any direct way as an essential part of any crystallization theory for polymers. Such behavior is impossible in other polymeric systems as the fold surface is the highest energy surface and the presence of folds prohibits growth on that surface. However, models of surface roughening, which were developed as an alternative explanation for the behavior of, principally, polyethylene, predict the conventional lamellar thickness - supercooling relation to exist, which is inconsistent with the observed existence of a constant lamellar thickness with variable crystal core dimensions.It is suggested that polyamide 66 be taken as a paradigm for a different kind of polymer crystallization than that normally encountered. That is crystallization in which the growth face is the highest energy surface, not the folded chain surface, having much in common with the behavior of non-polymeric materials. The energetic changes occurring in this case, however, are governed by a combination of entropic and enthalpic barriers to crystallization, rather than being dominated by enthalpic considerations, as in metals. This is a direct result of the entropic effects of the long chain nature of polymers combined with the enthalpic effects of the hydrogen-bonding.     

Hydration of sulfonated polyimide membranes. II. Water uptake and hydration mechanisms of protonated homopolymer and block copolymers

The hydration of sulfonated polyimide membranes in their protonated form is probed by infrared spectrometry using a recently described method. The membranes considered are the homopolymer, made of identical sulfonated repeat units, and two block copolymers composed of these units plus similar ones with no sulfonic groups in two different proportions. The experiments consist of registering series of spectra of these membranes at various hygrometries of the surrounding atmosphere. The quantitative analysis of the evolution of these spectra allows one to measure precisely the water uptake and to define in terms of chemical reactions the various hydration mechanisms that are active at a definite value of the hygrometry. It shows how the dried homopolymer significantly differs from the two dried block copolymers: in the homopolymer, a good proportion of SO(3)H groups that represent 83% of sulfonate groups, cannot establish H-bonds on C=O groups that are in a relatively small number. As a consequence, all coexisting SO(3)(-) groups are H-bonded to single H(3)O(+) cations with no extra H(2)O molecules. In both dried block copolymers, each SO(3)H group (60% of the sulfonate groups) establishes H-bonds on C=O groups that are in a sufficiently great number. These H-bonds stabilize these SO(3)H groups, and coexisting SO(3)(-) groups are H-bonded to cations that are found in the form of H(5)O(2)(+) or H(7)O(3)(+) that contain several H(2)O molecules. When the hygrometry increases, these differences get less marked but can be precisely defined.     

Chemical and electrochemical synthesis of homopolymer and copolymers of 3‐methoxyethoxythiophene with aniline,thiophene and pyrrole for studies of their gas and vapour sensing

Herein we report chemical and electrochemical formation of poly(3‐methoxyethoxythiophene) and its copolymers with aniline, thiophene and pyrrole which give highly conducting polymeric materials. These are soluble in common organic solvents in the conducting state. The response mechanism of these compounds, to a selection of gases and vapours, was investigated using two techniques: measurement of conductance and mass changes using a four probe method and X‐ray fluorescence (XRF) device, respectively. Prepared films were exposed to hydrogen halides, hydrogen cyanide, halogens, monochloroacetic acid (MCAA), 1‐3‐5 trichloromethylbenzene (TCMB), methylbenzyl bromide (MBB), bromoacetone (BA) and cyanogen bromide (CB). These gas sensors may have advantages compared to other sensors in their ability to operate at room temperature, low concentration, stability in air, sufficient diffusion and their selectivity. Copyright © 2001 John Wiley & Sons, Ltd.     

Difference in lower critical solution temperature behavior between random copolymers and a homopolymer having solvatophilic and solvatophobic structures in an ionic liquid

The solubility and phase behavior of poly(benzyl methacrylate) (PBzMA) and poly(styrene-co-methyl methacrylate) (P(St-co-MMA)) in a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfone)imide ([C(2)mim][NTf(2)]), have been explored as a function of temperature. Although both polymers have solvatophobic phenyl groups and solvatophilic methacrylate groups in the structure, their distribution on the polymer chains is quite different. In PBzMA, both structures are incorporated in each monomer unit, whereas in P(St-co-MMA)s the distribution is statistically determined by the monomer reactivity ratio of St and MMA. Both polymer solutions in [C(2)mim][NTf(2)] become turbid with an increase in temperature (lower critical solution temperature (LCST) behavior). The turbidity change occurs sharply at 100 degrees C for PBzMA, whereas it is sluggish for P(St-co-MMA)s. The LCST-type phase-separation temperature for P(St-co-MMA)s decreases with an increase of the St composition. The sluggish phase separation for P(St-co-MMA)s has been explained in terms of the presence of the MMA sequences along the polymer chain, which inhibits the St aggregation to a certain extent. The dynamic light scattering (DLS) measurements for PBzMA reveal that the hydrodynamic radius of PBzMA suddenly changes at 100 degrees C; below this temperature, no aggregation is observed. This result strongly implies that the coil-to-collapse transition is of the first-order type. It has been demonstrated that the LCST-type phase separation of the polymers in an ionic liquid is greatly affected by the distribution of the solvatophilic and solvatophobic groups on the polymer chains.     

Dewetting behavior of a block copolymer/homopolymer thin film on an immiscible homopolymer substrate

Numerous previous studies have established that the addition of a microphase-ordered AB diblock copolymer to a thin homopolymer A (hA) film can slow, if not altogether prevent, film rupture and subsequent film dewetting on a hard substrate such as silica. However, only a few reports have examined comparable phenomena when the hA/AB blend resides on a soft B-selective surface, such as homopolymer B (hB). In this work, the dewetting kinetics of thin films composed of polystyrene (PS) and a symmetric poly(styrene-b-methyl methacrylate) (SM) diblock copolymer on a poly(methyl methacrylate) substrate is investigated by hot-stage light microscopy. Without the SM copolymer, the dewetting rate of the PS layer is constant under isothermal conditions and exhibits Arrhenius behavior with an apparent activation energy of approximately 180 kJ/mol. Addition of the copolymer promotes a crossover from early- to late-stage dewetting kinetics, as evidenced by measurably different dewetting rates. Transmission electron microscopy reveals the morphological characteristics of dewetted PS/SM films as functions of film thickness and SM concentration.     

Melt crystallized polyamide 6.6 and its copolymers, Part I. Melting point - Lamellar thickness relations in the homopolymer

The effect of isothermal crystallization temperature and time on the lamellar thickness and the melting behavior of polyamide 66 has been studied. Measurements were made of the melting temperature, crystallinity, and the long period. When calculated in the conventional direct manner, for samples crystallized isothermally, the calculated lamellar thickness was found to vary only from 2.4 to 3.2 nm over the entire range of conditions considered. When viewed in a non-critical fashion the polymer appears to conform to normal behavior including typical T_c vs. T_m behavior on a Hoffman-Weeks plot and apparent linearity in a Gibbs-Thompson plot. SAXS data indicates that there are only small changes in the lamellar thickness occurring over the entire crystallization range despite major changes in the melting point. Accordingly the Gibbs-Thompson plot shows major amounts of scatter, which are well beyond the experimental errors involved. The changes in melting temperature appear to be a result of changes in the structure of the fold surface on the basis of the conventional lamellar thickness analysis. In particular they appear to be due to changes in the character of the surface related to the hydrogen bonding and to the relative amounts of acid and amine segments present in the folds.When a more thorough analysis of the SAXS data are conducted, using a one dimensional correlation function approach, calculation of the crystal core thicknesses and “interfacial layer” thicknesses, a different picture emerges. In this case, the total lamellar thickness remains approximately constant at 2 repeat units in length with isothermal crystallization temperature, however, the core thickness increases with increasing crystallization temperature and time, from 1.5 to 2 repeat units in length, whereas the “interfacial layer” thickness is substantial at lower temperatures and times. When the core thickness is used in a Gibbs-Thompson plot the equilibrium melting temperature is found to be 303.7 °C (cf. 301 °C from solution grown crystals). However, the fold surface free energy is found to be 23.7 erg/cm² much lower than the value of 74.6 erg/cm² characteristic of solution grown crystals. Such a large discrepancy is believed to be a result of the highly polar solvents used in solution based studies generating the widely accepted “acid folds”. The difference may be because of a switch to folds containing six methylene groups from the diamine mer in the bulk case.Since the polymer is known to crystallize in the hexagonal state and reorganize during cooling to the regularly reported structure it is possible that the “interfacial thickness” is indeed a disordered surface layer within the crystalline lamella that originates from the precursor hexagonal phase during its formation, rather than the conventional disordered surface interpretation, applicable to polymers such as polyethylene. It is also possible that it is reflective of disorder induced in surface layers within the crystal due to the conformational changes occurring during this crystal-crystal transition. For these reasons, we prefer to refer to the “interfacial layer” obtained from SAXS calculations as an innerlayer.     

Self-assembly of homopolymer and copolymers of N-4-hydroxyphenyl-acrylamide with diazoresin via H-bonding attraction

A kind of photoactive multilayer utrathin films has been fabricated via H-bonding attraction from hydroxyphenyl containing polymers as H-donor and diazoresin (DR) as H-acceptor by means of a self-assembly technique. The layer-by-layer deposition of two components is monitored spectrometrically and shows that the UV-VIS absorbance of the film increases linearly both at 250 nm (absorption of benzene nucleus) and at 383 nm (absorption of diazonium group), which indicates that the fabrication proceeds regularly. The nature of H-bonding between layers was verified by the determination of IR spectra of the film fabricated directly on a CaF₂ wafer. The stability of the films toward polar solvents increases dramatically after UV irradiation of the films. It was confirmed provisionally that the bond nature between the layers of the film changes from H-bonding to covalent bonding under UV irradiation. The photodecomposition of the -N₂⁺ groups of the film under UV light follows first order reaction kinetics and a mechanism of the photoreaction has been tentatively proposed.     

Impact of diblock copolymers on droplet coalescence, emulsification, and aggregation in immiscible homopolymer blends

Using rheo-optical techniques, we investigated the impact of interfacial wetting of symmetric diblock copolymers (BCPs) on the coalescence and aggregation of polydimethylsiloxane (PDMS) droplets in immiscible polyethylene-propylene (PEP) homopolymers. Anionic polymerization was used to synthesize well-defined matrix homopolymers and symmetric 16 kg/mol-to-16 kg/mol PDMS-b-PEP diblock copolymers with low polydispersity (PDI ≈ 1.02) as characterized with size exclusion chromatography and nuclear magnetic resonance spectroscopy. Blends were formulated to match the viscosities between the droplets and the matrix. Moreover, molecular weights of these components were varied to ensure that the inner block of the copolymer inside the droplet was collapsed and dry, whereas the outer block of the copolymer outside of the droplet was stretched and wet. Droplet breakup and coalescence as well as interfacial tensions were measured using rheo-optical experiments with Linkam shearing stage and an optical microscope. Subsequent to droplet breakup at high shear rates, we found that the BCPs mitigated shear-induced coalescence at lower shear rates. Based on surface tension measurements, the stretching of the BCP increased in lower molecular weight matrices, causing the droplet surface to saturate at lower coverage in line with theoretical predictions. Droplet aggregation was detected with further reductions in shear rate, which was attributed to the dewetting or the expulsion of the matrix from a saturated brush. Ultimately, the regions of droplet coalescence and aggregation were scaled by balancing the forces of shear with those due to the attraction between BCP-coated droplets.     

Direct interchange reaction in a homopolymer melt. Evolution of the MWD: an analytical solution

Kinetics of a direct interchange reaction in a homopolymer melt is studied theoretically. Relaxation of the molecular weight distribution to its most probable (Flory) stationary form^[1] is considered. To this end, the time‐dependent generating function of the transient distribution is calculated analytically. Peculiarities of the relaxation process are investigated for two kinds of the initial distribution, namely, the sum of two Flory distributions with different number averages N₁ and N₁, and the delta‐function. The former case describes a blend of two polydisperse polymers whereas the latter corresponds to a monodisperse melt. In each case, the dependencies of the differential molecular weight distribution and the weight‐ and z‐average polymerization degrees on the number of interchanges per number average chain are obtained in the explicit form. Earlier studies of this problem are briefly discussed.     

The effect of copolymer composition on the dynamics of random copolymers in a homopolymer matrix

The effect of copolymer composition on the dynamics of random copolymers in a homopolymer matrix is studied using computer simulations within the framework of the bond-fluctuation model on blends containing low concentrations (10%) of A-B copolymers, where A and B are two different types of monomers, dispersed in a homopolymer matrix of chains with only A-type monomers. Four copolymer compositions were studied, phi(A)=0.33, phi(A)=0.5, phi(A)=0.66, and phi(A)=0.82, while maintaining a statistically random sequence distribution. For this study, we have only included intermolecular interactions between A and B monomers. Our results indicate, in agreement with experimental data, that copolymer composition has an impact on system dynamics. Analysis of the structure reveals that copolymers with majority A content are expanded in the homopolymer matrix, have fewer interchain copolymer-copolymer contacts, and are well dispersed in the homopolymer matrix. On the other hand, copolymers with lower A content form a more compact structure, have more interchain contacts, and form aggregates that are short lived. This in turn leads to slower system dynamics. Both the radius of gyration (Rg) and copolymer end-to-end vectors (Re) increase with increasing A content until phi(A)=0.66 and then decrease. Copolymers with lower A content form more compact structures as the repulsive interactions between unlike species are minimized by the copolymers folding back on themselves and forming aggregates of copolymer chains. Thus, these results provide insight into the variation of copolymer dynamics with composition in the system by documenting the correlation between the thermodynamics of this mixture, the conformation of a copolymer chain in a homopolymer matrix, and the dynamics of both components in this blend.     

Critical micelle concentrations of block and gradient copolymers in homopolymer: Effects of sequence distribution,composition, and molecular weight

The critical micelle concentrations (CMCs) of styrene–methyl methacrylate (S-MMA) block and gradient copolymers present in a homopolymer poly(methyl methacrylate) (PMMA) matrix were determined using an intrinsic fluorescence technique based on the ratio of excimer to monomer fluorescence from styrene repeat units. The homopolymer molecular weight (MW) and copolymer MW, composition, and sequence distribution were varied to determine their effects on the CMC, and comparisons were made to theory. Although the effects of these parameters on micelle formation have been the focus of significant theoretical study, few experimental studies have addressed these issues. The MW of the S block (forming the micelle core) has a strong effect on the CMC. For example, an order of magnitude reduction in the CMC (from ∼ 1 to ∼ 0.1 wt %) is observed when the S block MW is increased from 51 to 147 kg/mol while maintaining the MMA block and PMMA MWs at 48–55 kg/mol. Increasing the PMMA matrix MW also has a strong an effect on the CMC, with the CMC for a nearly symmetric S-MMA block copolymer with each block MW equal to 48–51 kg/mol decreasing by a factor of 5 and by several orders of magnitude when the matrix MW is increased from 55 to 106 kg/mol and 255 kg/mol, respectively. In contrast, similar changes in the MMA block MW have little effect on the CMC. Finally, when present in a 55 kg/mol PMMA matrix, a 55 kg/mol S-MMA gradient copolymer with a styrene mole fraction of 0.51 exhibits a factor of 6 larger CMC than a block copolymer of similar MW and composition. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2672–2682, 2008     

Thermal stability of poly(acryloyl chloride) homopolymer and copolymers of acryloyl chloride with methyl methacrylate

The thermal stabilities of poly(acryloyl chloride) homopolymer and copolymers of acryloyl chloride with methyl methacrylate covering the entire composition range were studied by thermogravimetric analysis. At each extreme of the composition range incorporation of comonomer units results in a copolymer which is less stable than the PMMA homopolymer. The activation energies of the decomposition of the copolymers were calculated using the Arrhenius equation and found to decrease from 32.2 to 12.5 kJ mol^?1 as acryloyl chloride concentration of the copolymer increases, indicating that the copolymers of higher acryloyl chloride concentration should easier decompose than other copolymers. The reactivity ratios of the copolymer were calculated and found to ber ₁(AC)=0.2±0.02 andr ₂(MMA)=0.9±0.1.     

Vinyl copolymers containing pendant 1,3,4-oxadiazole chromophores: Preparation and electrochemical and electroluminescent properties

Three vinyl copolymers (P1–P3) containing pendant aromatic 1,3,4-oxadiazole derivatives were prepared from their precursor poly(styrene-ran-4-vinylbenzyl chloride) (weight-average molecular weight = 11,400, polydispersity index = 1.18), which had been synthesized by controlled radical polymerization (reversible addition–fragmentation chain transfer). The copolymers were readily soluble in common organic solvents and were basically amorphous materials with 5% weight loss temperatures higher than 360°C. The photoluminescence spectroscopy results revealed that the architectures of P2 and P3 suppressed aggregate formation in the solid state. The LUMO levels of P2 (−3.10 eV) and P3 (−3.09 eV), estimated from cyclic voltammetry data, were much higher than that of P1 (−3.81 eV). The HOMO levels were in the order of P3 (−5.37 eV) > P2 (−5.77 eV) > P1 (−5.96 eV). However, both the HOMO and LUMO levels of P1–P3 were much lower than that of poly[2-methoxy-5-(2′-ethylhexoxy)-p-phenylenevinylene] (MEH-PPV) because of the electron-withdrawing characteristics of the pendant aromatic 1,3,4-oxadiazole groups. The luminance (5860 cd/m²) and current efficiency (1.45 cd/A) of an electroluminescence device [indium tin oxide/poly(3,4-ethylene dioxythiophene)/MEH-PPV/Al] were improved significantly to 16,261 cd/m² and 4.79 cd/A, respectively, through blending with P2 (50/50). This study suggests that copolymers P1–P3 are versatile materials for electron-transport/injection applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2259–2272, 2007     

Intermolecular biological electron transfer: an electrochemical approach.

We investigated the electron transfer (ET) rates between a well-defined gold electrode and cytochrome c immobilized at the carboxylic acid terminus of alkanethiol self-assembled monolayers (SAMs) by using the potential modulated electroreflectance technique. A logarithmic plot of ET rates against the chain length of the alkanethiol is linear with long chain alkanethiols. The ET rates become independent of the chain length with short alkanethiols. It is proposed that the rate-limiting ET step through short alkyl chains results from a configurational rearrangement process preceding the ET event. This "gating" process arises from a rearrangement of the cytochrome c from a thermodynamically stable binding form on the carboxylic acid terminus to a configuration, which facilitates the most efficient ET pathways (surface diffusion process). We propose that the lysine-13 of mammalian cytochrome c facilitates the most efficient ET pathway to the carboxylate terminus and this proposal is supported by the ET reaction rate of a rat cytochrome c mutant (RC9-K13A) [Elektrokhimiya (2001) in press], in which lysine-13 is replaced by alanine. The ET rate of K13A is more than six orders of magnitude smaller than that of the native protein.     

Antimicrobial and hemolytic activities of copolymers with cationic and hydrophobic groups: a comparison of block and random copolymers

Random and diblock copolymers of 2-(N,N-dimethylamino)ethyl methacrylate and butyl methacrylate are prepared by ATRP. As mimics of cationic antimicrobial peptides, the random and diblock copolymers show similar antimicrobial activities. In contrast, the diblock copolymers have much lower hemolytic activities than the random copolymers. The cell selectivity (HC(50)/MIC, where HC(50) is the concentration to lyse 50% of human red blood cells and MIC is the minimum concentration to inhibit bacterial growth) of the diblock copolymers are 150 to 27,500 times higher than that of random copolymers with similar compositions.