Conformational behavior of styrene–dymethylsiloxane block copolymers in dilute solution

To determine the behavior of a copolymer is dilute solution, a viscosity study has been performed on a polystyrene–polydimethylsiloxane block copolymer in three solvents presenting different thermodynamic conditions. The results are discussed in relation to a mixture of homopolymers and a segregated model. The unperturbed dimensions, obtained by the Stock–mayer–Fixman method, are intermediate between those of the parent homopolymers. The intrinsic viscosity measured in a good solvent, toluene, was close to the weighted averages of those of the corresponding homopolymers of equal molecular weight, but higher in decalin and in butanone, θ solvents for PS and PDMS, respectively. According to the low value obtained for the interaction parameter, the chain is slightly expanded as a result of the interactions between the unlike monomer units. Both segregation and random conformation would probably occur, depending on the quality of the solvent.     

Solution properties of styrene-p-chlorostyrene diblock copolymers—I. Conformational behaviour in dilute solutions

The conformational behaviour of styrene-p-chlorostyrene diblock copolymers in dilute solutions was studied and compared with that of the corresponding triblock copolymers. Eight styrene-p-chlorostyrene diblock copolymers, of almost equimolar composition but with different molecular weights, were prepared using an anionic polymerization technique. The intrinsic viscosities of the copolymers were measured in non-selective solvents, such as toluene and 2-butanone, and in a selective solvent, cumene. The osmotic second virial coefficients of the diblock copolymers were measured in toluene. The data were analysed on the basis of two parameter theories. The unperturbed dimensions for the diblock copolymers can be expressed as a composition average of those for the parent homopolymers and the long-range interaction parameters of the diblock copolymers in toluene, 2-butanone and cumene are smaller than those of the triblock copolymers of the same composition. It means that the diblock copolymer chains in these 3 solvents had a more compact conformation than the triblock copolymers of the same composition and molecular weight.     

Solution behavior of styrene–ethylene oxide block copolymers

Hydrophobic–hydrophilic water-soluble block copolymers were prepared by “living” anionic polymerization. They consist of a polystyrene block and a polyethylene oxide block. From data on solution viscosity and high-resolution NMR in water, the molecular dimensions of the two-blocks copolymers are found similar to that of polyethylene glycols of the same molecular weight in the same solvent. These block copolymers exhibit microphase separation.     

Polymeric complex membranes based on styrene–diene–styrene triblock copolymers for oxygen enrichment

Polymers containing a vinylpyridine, vinylimidazole or oxirane group could be used to immobilize cobalt Schiff bases (CoS), which serve as the oxygen carrier in oxygen enrichment. The graft copolymers, based on styrene–butadiene–styrene (SBS) and styrene–isoprene–styrene grafted with 4-vinylpryidine and 1-vinylimidazole, and epoxidized SBS copolymers were prepared to immobilize CoS. The equilibrium constants between CoS and polymeric materials, the oxygen coordination number and the oxygen binding constants were determined. The thermodynamic parameters of oxygen association/dissociation in various complex membranes were determined. The oxygen permeation behavior through various CoS-containing complex membranes was studied and discussed by the dual-mode facilitated transport theory. The permeation properties of oxygen and nitrogen at low pressure were also investigated.     

Dilute solution properties of styrene–acrylonitrile and styrene–methyl methacrylate copolymers. I. Intrinsic viscosity–molecular weight relations

Styrene–acrylonitrile (St–AN) copolymers of three compositions—27.4 mole-% (SA₁); 38.5 mole-% (SA₂); and 47.5 mole-% (SA₃) acrylonitrile—and styrene–methyl methacrylate (St–MMA) copolymer (SM) of 46.5 mole-% methyl methacrylate were prepared by bulk polymerization at 60°C with benzoyl peroxide as the initiator, and were then fractionated. The molecular weights of unfractionated and fractionated samples were determined by light scattering in a number of solvents. The [η] versus M?_w relations at 30°C were established for SA₁, SA₂, SM, and polystyrene (PSt) in ethyl acetate (EAc), dimethyl formamide (DMF), and γ-butyrolactone (γ-BL), and for SA₃ in methyl ethyl ketone (MEK), DMF, and γ-BL. Second virial coefficients A₂ and the Huggins constant were determined. From values of A₂ and the exponent a of the Mark–Houwink relation it is seen that the solvent power for samples SA₁, SA₂, and PSt is in the order EAc < γ-BL < DMF, while for sample SA₃ the solvent power is in the order MEK < γ-BL < DMF. The solvent power decreases with an increase in AN content. The solvent power of the three solvents used for SM copolymer sample is practically the same within experimental errors. From the a values it is concluded that in a given solvent the copolymer chains are more extended than the corresponding homopolymers.     

Geometric properties of micelles formed by triblock copolymers and solubilizates in dilute solutions

In this work we study the geometric properties of the triblock copolymer micelles with solubilized low-mass molecules in a selective solvent using the Monte Carlo technique on a cubic lattice. The triblock copolymers are of the ABA type, with the two insoluble blocks at the ends. The size of the micelles is characterized by the squared radius of gyration of the micellar core, R_g², while the shape is treated by the asphericity b and the acylindricity c, which are defined in terms of the principal moments of the radius of gyration tensor. The parameters varied are the amount of solubilizate molecules, the polymer concentration, the interaction parameters between A and B, A and solvent, solute and solvent, solute and B block, and the A and B block length. The micelle size, characterized by R_g², grows with increasing concentration of the solubilizates and/or the polymer, and stronger interactions between the incompatible species. The A block length is found not to modify R_g² monotonously, while an increase in B block length results in a decrease in R_g² at high concentrations. As the size expands, the micellar shape becomes less spherical but retains its cylindricity. In addition to an increase in the averaged R_g², the distribution of R_g² becomes broader and the system less homogeneous.     

Fractionation of styrene–acrylonitrile copolymers

Three types of commercial styrene–acrylonitrile copolymer were fractionated by coacervate extraction and by column-elution techniques. Both methods were studied with two different solvent–nonsolvent pairs. Glass wool was used as the support material in the column. Fractionation by the coacervate extraction method was studied with benzene–triethylene glycol as a solvent–nonsolvent system at 60°C and with dichloromethane–triethylene glycol at 25°C. Column elution was carried out with acetone–methanol as the solvent–nonsolvent system at 30°C, and with dichloromethane–methanol at 20°C. Results of excellent reproducibility were obtained by these two methods. Characterization of fractions involved determination of both the molecular weight and chemical composition. It was established that the fractionation of the samples tested was dependent upon molecular weight only. The two methods described above are compared. Each gives an efficient procedure for fractionation of styrene–acrylonitrile copolymers.     

Preparation of triblock styrene–tert-butylstyrene–styrene copolymers by living radical polymerization with a heterogeneous polymeric initiator

Triblock copolymers containing the sequence styrene, p-tert-butylstyrene, styrene were prepared in an emulsion system by using isotactic polypropylene hydroperoxide as the initiator together with triethylenetetramine as an activator, according to the method of Mikulasova and co-workers. Polymerization of styrene continued after removal of the initiator from the emulsion by filtration and eventually reached 100% conversion after 4 hr at 35°C. tert-Butylstyrene at 80°C and styrene at 35°C were added successively to the system, with each polymerization reaction carried to 100% conversion before the next monomer was added. Thin-layer chromatography was used to separate the homopolymers and block copolymers in order to determine the purity of the product. Monomer compositions of the block copolymers was verified by infrared analysis. The existence of two separate phases in the extracted block copolymer was indicated by the observation of two distinct glass transition temperatures.     

Molecular structure of synthetic rubber. I. Light-scattering properties of styrene–butadiene copolymers

The discrepancy between the values reported for the weight-average molecular weight and molecular weight distribution of cold-type styrene-butadiene rubber is examined. The results obtained indicate that aggregation of the rubber due to hydrogen bonding or cluster formation is not a contributing factor to the high weight-average molecular weights obtained. The very broad molecular weight distributions, the M?_w/M?_n of the order of 10–20, are attributable to the presence of a few per cent of very high molecular weight fraction microgel in samples polymerized to moderate conversions. This microgel has been removed to various degrees by several methods: (1) mastication, (2) treatment with CaSO₄, (3) ultracentrifugation, and (4) ultrafiltration. The nature of this microgel is examined in terms of its light-scattering property, intrinsic viscosity, and concentrated solution viscosity. The weight-average molecular weight obtained by light scattering on these samples after removal of microgel are lower by as much as an order of magnitude. The operational definition of the weight-average molecular weight, M?′_w, is therefore introduced, corresponding to the one obtained after removal of the microgel. It is suggested that the actual and the operational weight-average molecular weights be used in conjunction in the characterization of these copolymers.     

Intramolecular cyclization of styrene–p-divinylbenzene copolymers

Styrene has been copolymerized at low conversion with minor quantities of p-divinyl-benzene (p-DVB) in (10–15%) solution in toluene and cyclohexane. Under these conditions the molecular weight of the polystyrene formed in the absence of p-DVB was controlled by chain transfer, and the copolymerization coefficients of the styrene and the p-DVB agreed with previous work. Polymer molecular weights were studied as a function of conversion. At very low conversions the number-average (2.2 × 10⁵) and the weight-average (4.4 × 10⁵) molecular weights were unaffected by substituting some of the styrene by p-DVB, but as the reaction continued M?_n increased slowly and M?_w much faster. On the other hand, even at the lowest conversions the intrinsic viscosity was drastically reduced by the introduction of p-DVB, and the radius of gyration, as measured by light scattering, fell. Infrared studies on the polymer show that the concentration of pendent double bonds in low-conversion copolymers is about half of the doubly substituted phenyl groups. It is concluded that the first polymer chains formed are extensively cyclized with the formation of a relatively large number of small rings.     

Epoxidation of polybutadiene and styrene–butadiene triblock copolymers with monoperoxyphthalic acid: Kinetic and conformation study

The rates of epoxidation of polybutadiene homopolymers and styrene–butadiene triblock copolymers with monoperoxyphthalic acid were measured at four temperatures in homogeneous solution. Dioxane and mixed solvents with chloroform were used as reaction media. Activation energy values were also calculated for polymers different in microstructure and styrene content. Viscometry in a modified viscometer was performed and combined with kinetic measurement to monitor the conformational change during epoxidation. Cis-content in polybutadiene and styrene content in SBS exhibit only slight effect on epoxidation in dioxane. The addition of chloroform promotes the reaction rate remarkably and enlarges the difference between polymers. Explanations were given including the solvent effect on reduced viscosity, which was used to correlate the conformational change of polymer chains. NMR and GPC analysis confirmed the absence of ring opening and degradation during epoxidation up to 54% epoxy group content.     

Temperature dependence of the fluorescence quantum yields of diphenylsiloxane‐based copolymers in dilute solutions

The monomer and excimer fluorescence quantum yields of well‐defined poly(dimethylsiloxane‐co‐diphenylsiloxane)s with different diphenylsiloxane (Ph₂SiO) contents have been determined, along with those of 1,1,3,3‐tetraphenyl‐1,3‐dimethyldisiloxane and 1,1,3,3,5,5‐hexaphenyltrisiloxane‐1,5‐diol used as model compounds, in a dilute organic solvent at different temperatures. The measured fluorescence quantum yields of the copolymers are correlated with the fraction of the ? (CH₃)₂SiO? (Ph₂SiO)_n? (CH₃)₂SiO? structures. The monomer fluorescence yield for copolymers with low Ph₂SiO contents is dominated mainly by the isolated ? (CH₃)₂SiO? (Ph₂SiO)? (CH₃)₂SiO? unit, and the apparent mean binding energy of the excimer does not increase significantly with increasing Ph₂SiO content. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 854–861, 2002     

New soybean oil‐styrene‐divinylbenzene thermosetting copolymers. III. Tensile stress–strain behavior

The tensile stress–strain behavior and fracture properties of some new soybean oil based polymeric materials were investigated at room temperature. These materials were prepared by the cationic copolymerization of regular soybean oil, low saturation soybean oil (LoSatSoy oil), or conjugated LoSatSoy oil with styrene and the diene comonomers divinylbenzene, norbornadiene, or dicyclopentadiene in a process initiated by boron trifluoride diethyl etherate (BF₃ · OEt₂) or related modified initiators. These new polymeric materials exhibited tensile stress–strain behavior ranging from soft rubbers through ductile to relatively brittle plastics. The Young's moduli of these polymers varied from 3 to 615 MPa, the ultimate tensile strengths varied from 0.3 to 21 MPa, and the elongation at break varied from 1.6 to 300%. These properties are obviously related to their crosslink densities. The conjugated LoSatSoy oil polymers had higher mechanical properties than the corresponding LoSatSoy oil and regular soybean oil polymers with the same stoichiometry. Some conjugated LoSatSoy oil polymers with appropriate stoichiometries showed yielding behavior in the tensile test process. A variety of new polymer materials can thus be prepared by varying the stoichiometry, the type of soybean oil, and the crosslinking agent. These soybean oil based polymers possessed mechanical properties comparable to those of commercially available rubbery materials and conventional plastics and thus may serve as replacements in many applications. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 60–77, 2001     

Ordered structures of styrene–butadiene block copolymers

Anionically prepared block copolymers of butadiene and styrene exhibit solution properties which result from a two-dimensional ordering of the polymer molecules. The most notable of these properties is the iridescent colors of toluene solutions which are dependent on concentration and abruptly change on mechanical deformation. Electron micrographs of the surface of cast films indicate that the ordered structure is retained to some degree in the solid state.     

Flexibilized styrene‐N‐substituted maleimide copolymers. I. Multiblock copolymers prepared from styrene‐maleimide telechelics and polytetrahydrofuran

Telechelic copolymers of styrene and different N‐substituted‐maleimides (SMIs) with a molecular weight of 2000–8000 g/mol were synthesized using the starved‐feed‐reactor technique and were nearly bifunctional when the monomer feed had a high styrene concentration. The COOH‐terminated rigid SMI blocks were polycondensated with OH‐terminated poly(tetrahydrofuran) (PTHF) blocks, with a molecular weight of 250–1000 g/mol, which are the flexible parts in the generated homogeneous multiblock copolymer. The entanglement density, which is closely related to the toughness of materials, increased in these flexible SMI copolymers (ν_e = 5.2 · 10²⁵ m⁻³) compared to the unflexibilized ones (ν_e = 2.4 · 10²⁵ m⁻³). The glass transition temperature of these flexibilized, single‐phase multiblock copolymers was still high enough to qualify them as engineering plastics. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3550–3557, 2000     

Macroreticular resins. III. Formation of macroreticular styrene–divinylbenzene copolymers

Experimental evidence is presented that describes the mechanism of formation of macroreticular styrene–divinylbenzene copolymers in which phase separation occurs during a suspension polymerization. The mode of formation of the macroreticular structure is described as a three-stage process in which each droplet of the organic phase behaves as an individual in a bulk polymerization that results in a bead of copolymer. Macroreticular structure formation is described by changes in copolymer swelling ratios, infrared absorption spectra of vinyl groups pendent to the polymeric matrices, surface area, total porosity, and pore-size distribution. The proposed mechanism of formation is also substantiated by electron micrographs of the copolymers during various stages of the copolymerization.     

Thermodynamics of plasticized triblock copolymers. I. Theory

The thermodynamic theory of bulk ABA copolymers developed by Leary and Williams is extended to copolymer–solvent systems. Free energy expressions are derived for five hypothetical phase-separated morphologies and evaluated specifically for a polymer with approximately 25% of the A component. The separation temperature, T_s, at which a given morphology will be in equilibrium with a homogeneous mixture, is also evaluated. The major result is the prediction of the T_s(?S) depression, where ?s is the solvent fraction. Depression is maximized when δ_S is equidistant between δ_A and δ_B, but becomes rapidly less when δ_S is outside the δ_A–δ_B range. Morphological favoritism is independent of ?_S and δ_S (model does not apply to preferential precipitation), with a planar microstructure being favored along with microstructures containing domains of B in continuous A for the 25% A polymer.     

Crazing in thin films of styrene–butadiene–styrene block copolymers

The mechanism of craze initiation and growth and its relationship to mechanical properties has been studied in thin films of styrene–butadiene–styrene (SBS) block copolymers. Optical microscopy and transmission electron microscopy were used to examine three copolymers which has a spherical rubber domain morphology but varied in rubber content from 20 to 50%. With increasing rubber content, the crazes became longer and less numerous. Widening of the crazes was at least partially responsible for the higher strains achieved in the copolymers, especially for the composition with the highest rubber content where the crazes widened to form micronecks. Transmission electron microscopy revealed that craze initiation and growth at the craze tip occurred by cavitation in the polystyrene phase. Cavitation of the continuous phase rather than the rubber domains was attributed to the concentration of chain-end flaws in the polystyrene. Crazes in the block copolymers followed a meandering pathway and the boundaries between crazed and uncrazed material were indistinct. Incorporation of fibrillated rubber particles into the craze fibrils strengthened the craze. At higher rubber content, the craze widened in the stress direction by voiding and fibrillation, which produced a cellular morphology.