Crystallization kinetics of γ phase poly(vinylidene fluoride)(PVDF) induecd by tetrabutylammonium bisulfate

The phase transition behavior of poly(2-ethyl-2-oxazoline) (PEtOx) under complexation with star-shaped poly(acrylic acid) (PAA) having various arm numbers (two, three, four, and six) has been studied by turbidity and laser light scattering measurements. The change in cloud point temperature (T _cp) of PEtOx was monitored as a function of pH, ionic strength, and arm number of the star polyelectrolyte. The shift in T _cp to a lower value than that of pure PEtOx was more pronounced at pH 4.2 (pH?a), when the carboxylic acid groups are protonated as compared to pH 7.0 (pH?>?pK_a ), when the acid moieties are partially ionized. Dynamic light scattering showed that these complexes may have micellar core-shell type structure with a mean hydrodynamic radius (R _h) ranging from 12 nm to ～200 nm depending upon the temperature. Significant shift in T _cp was observed for six-arm star poly(acrylic acid) complexes at both pH values. This change in the T _cp is accredited to the differences in the driving forces of phase transition, including hydrogen bonding between carboxylic acid groups of PAA and the carbonyl moiety of PEtOx as well as the hydrophobic interactions.     

Compatibilizing effects of poly(styrene-graft-ethylene oxide) in blends of polystyrene and butyl acrylate polymers

The compatibilizing effect of poly(styrene-graft-ethylene oxide) in polystyrene (PS) blends with poly(n-butyl acrylate) (PBA) and poly(n-butyl acrylate-co-acrylic acid) (PBAAA) was investigated. No significant effects of the graft copolymer on the domain size were found in the PBA blends. By functionalizing PBA with acrylic acid, the average size of the polyacrylate domains was reduced considerably by the graft copolymer. Thermal and dynamic mechanical analysis of the PS/PBAAA blends revealed that the PBAAA glass transition temperature (T_g) decreased with increasing graft copolymer content. The effect of the graft copolymer in the PS/PBAAA blends can be explained by interactions across the interface due to the formation of hydrogen bonds between the poly(ethylene oxide) (PEO) side chains in the graft copolymer and the acrylic acid segments in the PBAAA phase. Hydrogen bonding was confirmed by IR analysis of binary blends of PEO and PBAAA. Partial miscibility in the PEO/PBAAA blends was indicated by a PEO melting point depression and by a T_g reduction of the PBAAA phase. The thermal properties of the PEO/PBA blends indicated only very limited miscibility. © 1996 John Wiley & Sons, Inc.     

Thermal analysis of poly(acrylic acid)/poly(oxyethylene) blends

Blends between poly(acrylic acid) and two different poly(oxyethylenes), (1) polyethylene glycol (PEG-1000) and (2) poly(oxyethylene) (20) sorbitan monooleate (Tween-80), were studied by differential scanning calorimetry. The glass transition temperatures, T_g, of the various compositions of these blends were found to follow Fox's equation. At room temperature, blends containing no more than 60% PEG-1000 were amorphous and exhibited only a single glass transition. For these blends with PEG-1000, the glass transition temperatures for the annealed samples were higher than for the quenched samples due to the formation of a PEG crystalline phase. It was also found that addition of an amorphous polymer such as poly(acrylic acid) significantly reduced the degree of crystallinity of a semicrystalline polymer such as poly(oxyethylene). The Tween-80 systems did not show phase separation at room temperature. The compatibility between this poly(acrylic acid) and this poly(oxyethylene) was attributed to hydrogen bonding and to the lower crystalline lattice energy of this poly(oxyethylene) through its effect on its ideal solution solubility. © 1993 John Wiley & Sons, Inc.     

Miscibility and viscoelastic properties of acrylic polyhedral oligomeric silsesquioxane-poly(methyl methacrylate) blends

We investigate the miscibility of acrylic polyhedral oligomeric silsesquioxanes (POSS) [characteristic size d≈2 nm] and poly(methyl methacrylate)(PMMA) in order to determine the effect of well-dispersed POSS nanoparticles on the thermomechanical properties of PMMA. Two different acrylic POSS species (unmodified and hydrogenated) were blended separately with PMMA at volume fractions up to ?=0.30. Both POSS species have a plasticizing effect on PMMA by lowering the glass transition temperature T_g and decreasing the melt-state linear viscoelastic moduli measured in small amplitude oscillatory shear flow. The unmodified acrylic-POSS has better miscibility with PMMA than the hydrogenated form, approaching complete miscibility for loadings ?<0.10. At a loading ?=0.05, the unmodified acrylic POSS induces a 4.9 °C decrease in the T_g of PMMA, far less than the 17.4 °C decrease in the glass transition temperature observed in a blend of 5 vol% dioctyl phthalate (DOP) in PMMA; however, the decrease in the glass transition temperature per added plasticizer molecule is nearly the same in the unmodified acrylic-POSS-PMMA blend compared with the DOP-PMMA blend. Time-temperature superposition (TTS) was applied successfully to the storage and loss moduli data and the resulting shift factors were correlated with a significant increase in free volume of the blends. The fractional free volume f₀=0.046 for PMMA at T₀=170 °C while for a blend of 5 vol% unmodified acrylic-POSS in PMMA f₀=0.057, which corresponds to an addition of 0.47 nm³ per added POSS molecule at ?=0.05. The degree of dispersion was characterized using both wide-angle X-ray diffraction (WAXD) and dynamic mechanical analysis (DMA). Diffraction patterns for both blend systems show clear evidence of phase separation at ?=0.20 and higher, but no significant phase separation is evident at ?=0.10 and lower. The storage modulus measured in DMA indicates appreciable phase separation for unmodified acrylic POSS loadings ?≥0.10, while no evidence of phase separation is present in the ?=0.05 blend in DMA.     

The effect of molecular weight and casting solvent on the miscibility of polystyrene-poly(α-methyl styrene) blends

The glass transition temperatures (T_g) have been measured for blends of polystyrene and poly(α-methyl styrene) in the molecular weight ranges: polystyrene, 2030 < M < 250 000, and poly(α-methyl styrene), 17 000 < M < 250 000. The presence of either one T_g or two has been used as a criterion to determine the miscibility of each blend over a range of compositions, and the T_gs were obtained from measurements of the temperature dependence of the heat capacities of the blends. A sinlge T_g was observed over the entire composition range for blends in which the component molecular weights were both less than 70 000 g mol^?1, when these were cast from toluene solutions. When propylene oxide solutions were used to prepare the blends, this limit dropped to M = 50 000 g mol^?1. By using the appearance of two T_gs as an indication that phase separation had taken place, it was possible to establish regions of miscibility and immiscibility as a function of casting solvent and molecular weight for both components. The change in heat capacity at the glass transition was measured and it was found that for miscible blends the heat capacity changes are similar to the calculated values, but for immiscible systems the measured change is smaller than expected.     

Miscibility and interactions in blends and complexes of poly(4-methyl-5-vinylthiazole) with proton-donating polymers

The miscibility and interactions in blends and complexes of poly(4-methyl-5-vinylthiazole) (PMVT) with poly(p-vinylphenol) (PVPh), poly(acrylic acid) (PAA) and poly(vinylphosphonic acid) (PVPA) were studied. PMVT formed complexes with PVPA but not with PVPh and PAA. Each of the blends of PMVT with PVPh and PAA showed a single glass transition temperature (T_g), indicating miscibility. Fourier-transform infrared spectroscopic and X-ray photoelectron spectroscopic studies provided the existence of interactions in the PMVT blends and complexes. The XPS studies indicated that the thiazole nitrogen atoms are involved in hydrogen-bonding interactions with PVPh and PAA, and ionic interactions with PVPA. The sulfur atoms of PMVT also interact with PVPh, PAA and PVPA.     

The glass transition temperature of nitrated polystyrene/poly(acrylic acid) blends

Low-molecular-weight polystyrene was nitrated to different levels. The nitrated polystyrene was blended with different molecular weights of poly(acrylic acid), PAA. The glass transition temperatures (T_g) for the mixtures were investigated by differential scanning calorimetry. A single T_g was observed for all blends, indicating single-phase blends. In general, it was found that the T_g increases with molecular weight of PAA. The T_g values of the blends showed a positive deviation from the linear average T_g as a result of strong hydrogen bonding between the segments of the component polymers. The observed T_g values were not adequately represented by simple predictive equations or by single-parameter fitting equations. However, two-parameter fitting equations gave a reasonable representation of the data.     

Segmented polymer networks based on poly(N-isopropyl acrylamide) and poly(tetrahydrofuran) as polymer membranes with thermo-responsive permeability

Segmented polymer networks (SPNs) containing a polymer with a lower critical solution temperature were prepared by free radical copolymerization of poly(tetrahydrofuran) (PTHF) bis-macromonomers with N-isopropyl acrylamide (NIPAA). The PTHF bis-macromonomers, which were prepared by living cationic polymerization of tetrahydrofuran, were provided with acrylate or acrylamide end-groups by end-capping the living polymer chains with acrylic acid and 3-acrylaminopropanoic acid, respectively. Differential Scanning Calorimetry (DSC) experiments showed clearly that, for the same fractions of both network components, the phase morphology of the SPNs was highly influenced and adjustable by the nature of the end-groups of the bis-macromonomer as a result of their copolymerization behavior with NIPAA. For the same type of multi-component networks, the morphology changed from a heterogeneous up to a rather homogeneous nature by application of bis-macromonomers with, respectively, acrylate or acrylamide end-groups during their preparation. Swelling and DSC experiments on the swollen SPNs revealed, respectively, that the swelling properties and the cloud point temperature (T_cp) could be controlled by the network composition. The thermo-responsive water permeability and the possible application of the SPNs as pervaporation membranes for the separation of a water/isopropanol mixture were investigated as a function of temperature and network composition. The permeability and selectivity of the membranes decrease when the T_cp is reached. The permeability increases while the selectivity decreases with decreasing crosslink density or higher overall hydrophilicity of the SPNs.     

Design of novel poly(methyl vinyl ether) containing AB and ABC block copolymers by the dual initiator strategy

A new set of block copolymers containing poly(methyl vinyl ether) (PMVE) on one hand and poly(tert-butyl acrylate), poly(acrylic acid), poly(methyl acrylate) or polystyrene on the other hand, have been prepared by the use of a novel dual initiator 2-bromo-(3,3-diethoxy-propyl)-2-methylpropanoate. The dual initiator has been applied in a sequential process to prepare well-defined block copolymers of poly(methyl vinyl ether) (PMVE) and hydrolizable poly(tert-butyl acrylate) (PtBA), poly(methyl acrylate) (PMA) or polystyrene (PS) by living cationic polymerization and atom transfer radical polymerization (ATRP), respectively. In a first step, the Br and acetal end groups of the dual initiator have been used to generate well-defined homopolymers by ATRP (resulting in polymers with remaining acetal function) and living cationic polymerization (PMVE with pendant Br end group), respectively. In a second step, those acetal functionalized polymers and PMVE-Br homopolymers have been used as macroinitiators for the preparation of PMVE-containing block copolymers. After hydrolysis of the tert-butyl groups in the PMVE-b-ptBA block copolymer, PMVE-b-poly(acrylic acid) (PMVE-b-PAA) is obtained. Chain extension of the AB diblock copolymers by ATRP gives rise to ABC triblock copolymers. The polymers have been characterized by MALDI-TOF, GPC and ¹H NMR.     

Poly (acrylic acid) and poly (sodium styrenesulfonate) compatibility by Fourier transform infrared and differential scanning calorimetry

Blends of poly(acrylic acid) (PAA) and poly(sodium styrene sulfonate) (PSSNa) were prepared from polymer solutions by solvent evaporation. The observed decrease in PAA-solution pH upon addition of PSSNa suggests an inter-penetration of the two polymer chains, thus the polymer compatibility, in solution. The blend compatibility was studied with the attenuated total reflection-Fourier transform infrared (atr-FTIR) and the differential scanning calorimetry (DSC) techniques. The unique and composition-dependent glass transition temperature indicates that the two polymers are compatible, but the ΔT_g broadening suggests a certain degree of nano-heterogeneity. The T_g of pure PSSNa which was non-detectable in DSC, was calculated from the Fox equation. From FTIR data, the polymer compatibility could be attributed to the establishment of hydrogen bonds, and dipole-ion interactions between carboxylic groups, sulfonate groups, and sodium ion on the polymer segments.     

Effect of molecular oxygen on the n.m.r. relaxation times of some aromatic polymers

Proton spin-lattice (T₁) and spin-spin (T₂) relaxation times are reported for poly(2-vinylpyridine), poly(1-vinylanthracene) and polycarbonate in air, oxygen and in vacuo. The results substantiate earlier findings that oxygen complexes with the aromatic rings giving rise to T₁ minima which are not intrinsic to the polymers. This effect appears to be fairly general for aromatic containing polymers. For those polymers containing low temperature relaxations intrinsic to the polymer, the oxygen paramagnetic effect can complicate the relaxation behaviour and, in some cases, totally mask the intrinsic processes. The transitions in T₁ and T₂, due to the torsional oscillation of the anthracene side group in poly(1-vinylanthracene), is much better defined than the corresponding transitions for previously reported aromatic vinyl polymers. The activation energy for the motion of the side group is comparable to that of polystyrene and poly(N-vinylcarbazole).     

Characterization of aqueous micellar solutions of amphiphilic block copolymers of poly(acrylic acid) and polystyrene prepared via ATRP. Toward the control of the number of particles in emulsion polymerization

A series of diblock, triblock and star-block copolymers composed of polystyrene and poly(acrylic acid) were synthesized by ATRP. The structure of the copolymers, the size of the blocks and the composition were varied, keeping however a short polystyrene block and a poly(acrylic acid) content larger than 60 mol% to allow solubility in alkaline water. Their micellization was studied by static and dynamic light scattering and the influence of their structural characteristics on the aggregation number, N_agg, was examined at low salt concentration and alkaline pH. It was shown that micelles were in thermodynamic equilibrium and that N_agg followed the power law N_agg∼N_A^−0.9N_S² (with N_A, the total number of acrylic acid units in the copolymer and N_S, the total number of styrene units), that is characteristic of amphiphile micelles formed from strongly segregated block copolymers. Moreover, N_agg was independent of salt concentration in the investigated range. The same copolymers were previously used as stabilizers in emulsion polymerization [Macromolecules 34 (2001) 4439]. The final latex particle concentration, N_p, was compared with N_m, the initial micelle concentration. This enabled us to conclude that among the block copolymers studied, those with high acid content behaved like low molar mass surfactants. In contrast, those with low acid content formed stable micelles that could be directly nucleated to create latex particles, allowing a good control over N_p.     

Viscoelastic behavior of highly crosslinked poly(acrylic acid)

The effects of crosslinking upon the dynamic mechanical properties and swelling behavior of poly(acrylic acid) (PAA) have been studied. Materials were prepared by the free radical copolymerization of acrylic acid with varying amounts of the tetrafunctional monomer allyl acrylate (ALA). The results indicated a linear dependence of the glass-transition temperature (T_g) on composition, T_g increasing by ～43°C over the mole fraction range X = 0?0.37 ALA. Room temperature (25°C) modulus values, as determined by both dynamic and compression methods, were inversely proportional to the initial concentration of ALA. The degree of network formation has been characterized in terms of the molecular weight between crosslinks M_c, and the influence of this parameter on the swelling ratio was discussed.     

Molecular motion of poly(methyl methacrylate), polystyrene and poly(propylene oxide) in solution studied by 13C n.m.r. spin-lattice relaxation measurements: effects due to distributions of correlation times

The ¹³C n.m.r. spin lattice relaxation times and Nuclear Overhauser Enhancements have been measured for solutions of poly(methyl methacrylate) (PMMA) in o-dichlorobenzene, polystyrene (PS) in pentachloroethane and poly(propylene oxide) (PPO) in CDCI₃ as a function of temperature. For PS and PMMA a T₁ minimum is observed close to ambient temperature. The single correlation time theory of relaxation is inadequate to explain the relaxation data, but within experimental error, the data can be interpreted in terms of either the Cole-Cole distribution of correlation times, the log ?χ² distribution or a conformational jump model of chain dynamics.     

Brillouin scattering from oligomers of polydimethylsiloxane and the assignment of the hypersonic a loss peak in polymers

Hypersonic sound speed and loss have been measured in poly(dimethylsiloxane) fluids of viscosities 0.65 to 3.5 × 10⁴ centistoke. Both rise to a plateau level for viscosity values in excess of ～10 centistokes. Loss measurements as a function of temperature indicate that the α loss temperature (T_α) in the dimer is depressed below 180K compared to 230K in the high molecular weight materials. This molecular weight dependence of T_α is used to account for the hypersonic loss as a function of molecular weight in polystyrene and polypropylene glycol in addition to the assignment of the α loss peak in polydimethylsiloxane.     

A study of blending and complexation of poly(acrylic acid)/poly(vinyl pyrrolidone)

Poly(acrylic acid) (PAA) and poly(vinyl pyrrolidone) (PVP) were chosen to prepare polymer complex and blends. The complex was prepared from ethanol solution and the blends were prepared from 1-methyl-2-pyrrolidone solution. DSC results show that the T_gs of the PAA/PVP blends lie between those of the two constituent polymers, whereas T_g of the PAA/PVP complex is higher than both blends and the two constituent polymers. TGA results show that degradation temperature, T_d, of PAA increases upon adding PVP in the blend, but thermal stability of the complex is higher than that of the blends as reflected by the higher T_d. Both FTIR and high-resolution solid state NMR show strong hydrogen bonding between PAA and PVP by showing significant chemical shift. The T_1ρ(H) measurement shows that the homogeneity scale for the blend is at ∼20 Å and that for the complex is ∼15 Å.     

Copolymers of poly(2,6-dimethyl-1,4-phenylene ether) and ester units

Copolymers of telechelic poly(2,6-dimethyl-1,4-phenylene ether) segments with terephthalic methyl ester endgroups (PPE-2T, 3700 g/mol) and different diols were made via a polycondensation reaction. The terephthalic endgroups of PPE-2T are stable during this reaction. The T_g of these polyether-ester copolymers decreases with increasing diol length and diol flexibility. The T_g can be set between 100 and 200 °C by changing the type of diol. However at increasing diol length the T_g becomes broader and the test bars are less transparent because the extent of phase separation increases with increasing diol length. Only polymers with a diol length up to C12 are homogeneous. Phase separation is probably enhanced by the bimodal molecular weight distribution of PPE-2T. Phase separation can be suppressed by using shorter PPE-2T segments with a short diol. It is even better to use fractionated, monomodal PPE-2T. Copolymerisation is much more effective in decreasing the T_g of PPE and therefore its processability than blending with polystyrene. It is expected that the processability of these copolymers is much better than that of PPE.     

Effect of chain rigidity on block copolymer micelle formation and dissolution as observed by 1H-NMR spectroscopy

Amphiphilic copolymers poly(methyl methacrylate-b-acrylic acid), poly(methyl methacrylate-b-methacrylic acid), poly(methyl acrylate-b-acrylic acid) and poly(methyl acrylate-b-methacrylic acid) were prepared by reversible addition fragmentation chain-transfer (RAFT) polymerization. The hydrophilic polyacid blocks were either synthesized directly or formed by the hydrolysis of poly(tert-butyl acrylate) or poly(tert-butyl methacrylate) blocks. The hydrophobic blocks consisted of either the more rigid, high glass transition temperature (T _g ) poly(methyl methacrylate) or more flexible, low T _g poly(methyl acrylate) material. The hydrophilic blocks were either poly(methacrylic acid) (rigid, high T _g ) or poly(acrylic acid) (flexible, low T _g ). The micellization behavior of the polymers was studied by proton nuclear magnetic resonance (¹H-NMR) spectroscopy in mixtures of 1,4-dioxane-d₈ and D₂O. All four polymers were soluble in neat dioxane. In solutions of higher water content, the polymers with the more rigid hydrophobic blocks formed into micelles as was evidenced by broadening of the resonances resulting from the protons in those blocks. At moderate water concentration (25–50%), dissolution of the micelles was observed upon heating the solution. No micellization was observed in polymers containing the less rigid poly(methyl acrylate) hydrophobic block regardless of the identity of the hydrophilic block. As further evidence of micellization formation and dissolution, the spin-lattice (T ₁) and spin-spin (T ₂) relaxation times of protons in the hydrophobic and hydrophilic blocks were measured. Significant differences in the relaxation times as functions of temperature and solvent concentration were observed between the hydrophilic and hydrophobic blocks of the micelle-forming polymers.     

Some properties of styrene‐based ionomers. I

Some properties of styrene‐based ionomers containing alkali metal salts of acrylic acid or methacrylic acid have been investigated. A study has been conducted to examine the influence of the acidic content and nature (acrylic or methacrylic) and the nature of the alkali metal salt on the glass transition temperature, density, melt index and activation energy of a flow of the styrene‐based ionomers. The present studies have indicated that the temperature of glass transition (T_g) of sodium ionomers increases as the sodium content rises and the region of the glass transition broadens. The T_g's of the styrene‐acrylic acid (S‐AA) ionomers do not depend on the nature of the alkali metal introduced into the copolymer. The density of films rises with the content of acid or salt introduced to the polystyrene chain. The melt index of the investigated ionomers depends on the amount and type of the introduced acid and salt as well as on the molecular weight of the initial copolymer. The energy of activation of the flow is independent of the polymer molecular weight; however, the energy of activation of flow of the ionomers increases with larger ionic radii of the introduced alkali metal. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 55–62, 2003     

Effect of solvent or hydrophilic polymer on the hydration melting behavior of polyacrylonitrile

The effect of solvent, DMF, and hydrophilic polymer on the hydration melting behavior of Tae Kwang polyacrylonitrile-based copolymer (T-PAN) was investigated by DSC measurement. The melting temperature (T_m) of T-PAN was sharply lowered by incorporating water under autogenous pressure, but leveled off above a critical water content: 23 wt %. However, an additional incorporation of DMF into the hydrated T-PAN further lowered the T_m, even above the critical water content. On the other hand, addition of water-soluble poly(acrylic acid), poly(vinyl alcohol), and poly(ethylene glycol) or water-swellable starch to the hydrated PAN slightly raised the T_m. © 1994 John Wiley & Sons, Inc.