Properties of random and block copolymers of butadiene and styrene. I. Dynamic properties and glassy transition temperatures

The effect of monomer sequence on physical properties was investigated for butadienestyrene solution copolymers made by organolithium initiation. The polymers varied from random copolymers of uniform composition along the polymer chain to ideal block polymers of specific block sequence arrangement and included rubbers of intermediate degrees of randomness. Uniform composition random copolymers exhibit a single glass transition temperature and a very narrow dynamic loss peak corresponding to this transition. The glass transition can be predicted from the styrene content and the microstructure of the butadiene portion of the rubber. Random copolymers in which composition varies along the polymer chain, and to some extent between molecules, exhibit a single glass transition, but the dynamic loss peak is broadened. The extent of this broadening is shown to be compatible with the sequence distribution, polymer segments of various compositions losing mobility at different temperatures. This indicates a tendency for association between segments of different temperatures. This indicates a tendency for association between segments of different chains which are similar in composition. Block copolymers display two transitions, corresponding to T_g for each type of block. The position and width of the dynamic loss peaks are related to block length and compositional purity of the blocks.     

Melt flow and strength of branched styrene copolymers

In order to assess the dependence of strength properties of glassy polymers upon the extent of branching, copolymers of poly(styrene–acrylonitrile) were prepared. By using principally three methods: (a) hydroperoxide intermediates, (b) hydroxyl radical initiation, and (c) incorporation of transfer monomers, branched polymers with high levels of branching with comb and dendritic type structures were generated. The tensile strength was found to be strongly correlatable with melt flow, and, in general, the branched copolymers were found to have the same tensile strength as linear polymers of the same melt index.     

Volumetric properties of block and random copolymers of butadiene and styrene at pressures to 1 kilobar

Densities of thermally annealed copolymers were measured at 75° and 100°C at pressures to 1 kilobar. The compositions ranged from pure polybutadiene to pure polystyrene, from completely random to completely block copolymers. The experimental results are well represented by the Tait equation. To a first approximation, specific volumes and compressibilities are linear functions of weight per cent styrene. For a fixed composition, the effect of structure on volumetric properties is small. However, it appears that, when compared at the same overall composition, the specific volume and compressibility are larger for the random copolymer; specific volume and compressibility decline slightly when the styrene is in block rather than random form.     

Structure and properties of oil extended styrene butadiene block copolymers

The relationships between mechanical properties and structure of rapidly spin cast styrene-butadiene-styrene (SBS) block copolymers diluted with two different types of mineral oil are discussed. Small angle X-ray scattering (SAXS) measurements indicate that both oils go mainly into the rubbery polybutadiene phase. While during rapid spin casting the paraffinic oil improves the phase separation of polystyrene (PS) and polybutadiene (PB), the opposite is true for the aromatic oil. The measurements also suggest that the oils cause a preferential swelling of the superstructure along the longitudinal direction of the cylindrical PS domains. From this, it can be concluded that a larger number of interconnecting PB chains is present in the cross direction than in the longitudinal one. With increasing oil content, a further decrease of interconnecting chains in the latter direction may be the reason for the decrease of the tensile modulus. Furthermore, above a critical value of dilution (33 wt percent for paraffinic oil, 50 wt percent for the aromatic one), more and more spherical domains are formed instead of the cylindrical ones. This morphological transition explains the step present in the double logarithmic plot of the large strain tensile modulus as a function of oil dilution.     

Effects of gamma radiation on the dynamic mechanical and swelling behavior of styrene butadiene block and random copolymers

The physical structure of a number of styrene-butadiene copolymers were investigated via dynamic mechanical and swelling studies on uncrosslinked and gamma-radiation cross-linked films that had initially been solvent cast from toluene or methyl ethyl ketone. The mechanical behavior of these films before and after crosslinking was found to depend on the material history as well as the chemical structure of the copolymer, in agreement with observations made by other experimental techniques. A simple morphological interpretation was given to the dynamic mechanical spectra as a function of radiation dosage and a limited discussion of the swelling behavior is included.     

Properties of block versus random copolymers

Physical and mechanical properties of block copolymers are compared and correlated with the corresponding random copolymers. The important properties of melting point, transition temperatures, tensile strength, modulus, and elastic properties depend upon the structural arrangement of the molecular units comprising the polymer strecture. All available data suggest overwhelmingly that properties of block copolymers are superior to those of random copolymers. A block copolymer can have properties characteristic of each of the homopolymers from which it is derived as well as a set of properties due to the polymer strcture as a whole. Block copolymers have an advantage over random copolymers in that a crystalline polymer can be modified without significant reduction of its melting point, modulus, tensile strength, and elastic properties, and by suitable selection of a second component it affords a means of “building in” a particular property.     

Correlation between physical-mechanical properties and morphological features of cruciform styrene - butadiene block copolymers

The structural and morphological characterization of a cruciform styrene-butadiene block copolymer of the (SB)₄Si type is reported together with the stress-strain properties of films prepared by compression moulding. The influence of the compression on the morphology (and therefore on the mechanical properties) are considered in detail because the structure of the specimen becomes particularly simple; it consists of polystyrene cylinders arranged perpendicularly to the compression plane. The rods lead to a semi-continuous polystyrene phase, so that the film exhibits the Mullins and hardening effects already observed for linear three block copolymers. Explanations for these phenomena are given, supported by optical observations and by electron microscopical views of sections cut after deformation.     

Some effects of monomer sequence on the viscoelastic behavior of random copolymers of butadiene and styrene

The copolymerization of butadiene and styrene by lithium alkyls can be regulated to give either random or block copolymers. The block copolymers exhibit characteristic mechanical behavior which is attributable to their two-phase domain structure. In random copolymers free of long sequences of styrene there exists, nevertheless, the possibility of varying the sequence distribution by changing the manner in which composition varies along the polymer chain. Since copolymers of butadiene and styrene differing sufficiently in composition are likewise incompatible and will form multi-phase systems, it is likely that microheterogeneity can exist in certain “random” copolymers. Five copolymers of monomer ratio 70 : 30 butadiene/styrene, varying from a uniformly randomized sample, in which composition was very nearly independent of conversion, to a block polymer containing 22% block styrene chemical analysis, were prepared for the present investigation. Composition vs. conversion data indicated that all but the last polymer were free of long styrene sequences, with the composition distribution (along the chain) broadening systematically throughout the remainder of the series. The melt viscosity of the unvulcanized copolymers was distinctly affected by sequence distribution effects. Thus, the temperature coefficient of the apparent viscosity was independent of shear stress only for the uniformly randomized copolymer. In all others temperature superposition of the non-NEWTON ian flow curves was impossible, the discrepancies becoming larger the broader the composition distribution. The results can be explained qualitatively by association effects attributable to a domain structure similar to that found in block polymers. When these copolymers were cross-linked with dicumyl peroxide at 153 °C and the dynamic properties of the networks examined, no clear evidence of a domain structure was found except in the block polymer. Only the latter exhibited more than a single loss maximum. Temperature-frequency reduction of the dynamic measurements was successful with all but the block polymer. Whereas the parameters C₁ and C₂ in the WILLIAMS -LANDEL -FERRY equation appear to change systematically with the degree of randomness, there is evidence that this is attributable to a slight systematic drift toward higher vinyl unsaturation with increasing randomization of the monomer sequence. Relaxation spectra calculated for 25 °C were very nearly the same for all four random copolymers. When the polymers were cross-linked by gamma radiation at room temperature, the resulting networks did show properties indicative of a domain structure in the compositionally more heterogeneous copolymers. It is proposed that compatibility of chain segments of varying composition at the temperature of cross-linking leads to a suppression of the domain structure in the peroxide-cured rubbers, as segments of different composition are joined together. Independent evidence from stress-optical measurements supports this interpretation. The present investigation permits the conclusion that differences in sequence distribution of butadiene-styrene copolymers have, at best, only very minor effects on the visco-elastic properties of conventional vulcanizates, provided the polymers contain no long sequences of styrene units, i.e., polystyrene blocks detectable by classical methods. This is not true of the low shear melt viscosity, which senses relatively small differences in the composition and/or sequence distributions of the uncured rubbers.     

N.m.r. studies of butadiene - styrene copolymers

An analysis of the ¹³C nuclear magnetic resonance spectra of copolymers of butadiene—styrene, both block or random type, shows the possibility of observing the microstructure of the copolymers themselves. The microstructure of the copolymers was analysed in terms of triads of monomeric sequences. The units present in the copolymers are of the type: trans-1,4-butadiene, cis-1,4-butadiene, 1,2-butadiene and styrene. An assignment for all the experimental bands observed is proposed on the basis of correlation with homopolymers as well as on the basis of the frequencies for the single triads, calculated by additivity rules.     

Phase structure of solution cast films of α-methylstyrene/butadiene/styrene block copolymers

The phase structure of solvent cast films of α-methylstyrene/butadiene/styrene of differing compositions was investigated using physical methods. Both dynamic mechanical and differential scanning calorimetry measurements exhibited a single high temperature transition at 150°C. The transition has been shown to originate from a composite domain of the two glassy end blocks. Light scattering measurements showed that these domains varied in size from 0·35 to 0·40 μm and that they are randomly arranged within the butadiene matrix. The results are compared with the results of similar studies of ABA systems.     

Synthesis of structured nanoparticles of styrene/butadiene block copolymers via RAFT seeded emulsion polymerization

The structured nanoparticles of styrene (St) and butadiene (Bd) block copolymers were prepared by RAFT seeded emulsion polymerization of butadiene. It was confirmed that the block copolymers of PSt-b-P(St-co-Bd) was formed with controlled molecular weight and rather low PDI at low composition of the P(St-co-Bd) segment. With more incorporation of butadiene, the branching reaction of polybutadiene became obvious, leading to higher PDI and positive deviation of M_n from the theoretical predication. At the gel point, the composition of the P(St-co-Bd) segment was estimated to be 0.72. After this, the gel fraction increased quickly. The morphology of structured nanoparticles could be largely tuned simply by the copolymer composition. With the composition of the P(St-co-Bd) segment increased from 0.37 to 0.92, the morphology within the structured particles changed from the polybutadiene domains-in-polystyrene matrix, perforated concentric-spherical layer, concentric-spherical multi-layers, bi-continuous, to broken layers of polystyrene in polybutadiene matrix. It was found that the morphology of the block copolymer within nanoparticles was dependent on d/L values, which was in excellent agreement with the theoretical prediction.     

Solution styrene butadiene copolymers with lithium alkyl initiators

This paper is a review of the alkyllithium system of the copolymerization of butadiene and styrene. The alkyllithium system offer a very versatile tool by which a wide variety of styrene butadiene copolymers can be made to fit a particular application. Included are discussions of block and non-block copolymers of styrene butadiene, copolymers with functional groups, and copolymers with varying microstructure. In addition, wear and tractuion on a series of styrene butadiene copolymers with varying content and microstructure are presented.     

Nonlinear stress relaxation in palladium(II) complexes with triblock copolymers of styrene and butadiene

Above 200% strain, the mechanical response of triblock copolymers which contain styrene and butadiene is modified significantly by complexation with dichlorobis(acetonitrile)palladium(II). This pseudosquare‐planar transition metal salt forms π‐complexes with, and catalyzes the dimerization of, alkene groups in the main chain and the side group of Kraton's butadiene midblock. Between 10 and 100% strain, the plastic flow regime is similar for undiluted Kraton? and its Pd²⁺ complexes, but the level of engineering stress is approximately twofold larger for the complex that contains 4 mol % palladium(II) [Pd(II)]. Nonlinear stress relaxation measurements in the plastic flow regime (i.e., beyond the yield point but before the large upturn in stress) are analyzed at several different levels of strain. Transient relaxation moduli were modeled by a three‐parameter biexponential decay with two viscoelastic time constants. The longer relaxation time for Kraton? increases at higher strain, and in the presence of 4 mol % palladium chloride. A phenomenological model is proposed to describe the effect of strain on relaxation times. This model is consistent with the fact that greater length scales are required for cooperative segmental reorganization at larger strain. The resistance Ω to conformational reorganization during stress relaxation is estimated via integration of the normalized relaxation modulus versus time data. This resistance increases at higher initial jump strain because conformational rearrangements are influenced strongly by knots and entanglements at larger strain. The effect of strain on Ω is analyzed in terms of time‐strain separability of the relaxation modulus. Linear behavior is observed for Ω versus inverse strain (i.e., 1/ε), and the magnitude of the slope [i.e., ?dΩ/d(1/ε)] is threefold larger in the absence of PdCl₂(CH₃CN)₂. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1329–1336, 2004     

Melt viscosity characteristics of methacrylate–styrene copolymers

The activation energies of flow E_A of methacrylate–styrene copolymers containing n-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tridecyl, n-octadecyl, and cyclohexyl methacrylate have been investigated as a function of molecular weight, composition, and methacrylate monomer. Below a critical pendent group molar volume per chain unit (120 ± 10 ml Le Bas units), E_A was found to increase with molar volume; and above this value, a decrease in E_A was observed, reflecting a decrease in copolymer density. Copolymers with pendent group molar volumes per average chain unit of between 96 and 140 ml (Le Bas units) were found to exhibit sufficiently high E_A values to render them suitable for use in thermoplastic and photothermoplastic devices with superior development and erasure rates, at temperatures which enabled the attainment of the development and erasure viscosities with a low expenditure of heat energy. Methacrylate–styrene copolymers with long-chain ester methacrylates (viz., n-decyl and n-dodecyl methacrylate) were found to exhibit critical molecular weights M_c below 3000; and M_c was found to decrease with increasing methacrylate tail length and methacrylate concentration. These M_c values correspond to critical chain lengths Z_c below 45. Similar Z_c values have been previously reported for acrylonitrile–methyl methacrylate copolymers³⁰ and ethylene–propylene copolymers.²⁸     

Relationships between rheological properties,morphological characteristics,and composition of bitumen–styrene butadiene styrene copolymers mixes. II. A thermodynamical interpretation

The variations of the dynamic mechanical properties (at 5 Hz) of bitumen–SBS mixes in the function of their composition (polymer content, bitumen composition) have been established. The relationships between the viscoelastic measurements and the morphological characteristics, previously determined, have been used to interprete these variations in terms of change of morphological characteristics (phase composition, phase content in the blends). Finally, a theoretical approach based on the thermodynamics of mixing is proposed to explain the relationships between the composition and the morphological characteristics. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1609–1618, 1997     

Blends of styrene butadiene styrene TRI block copolymer/polyaniline-Characterization by WAXS

Electrically conductive blends based on polyaniline-dodecylbenzene sulphonic acid (Pani.DBSA)/styrene-butadiene-styrene (SBS) block copolymer have been prepared by two methods namely melt mixing and polymerization of aniline in the presence of SBS using in situ polymerization method. The influence of composition and synthetic methods on the performance of SBS/Pani blends was established. The obtained SBS/Pani blends have been characterized by mechanical, morphological and electrical properties. A great reduction in volume resistivity values with increase in Pani content was noticed for in situ polymerization method compared to melt mixing method. The microstructural parameters were also computed using Wide Angle X-ray Scattering (WAXS). The results are compared with mechanical and electrical properties.     

Diffusion of radioactively tagged penetrants through random and block styrene–butadiene copolymers and filled cis-polybutadiene

The diffusion of radioactively tagged n-hexadecane in trace amounts has been studied in 22 random styrene–butadiene (SBR) copolymers with different styrene contents and butadiene microstructures; in several SBR block copolymers with different average block lengths (also diffusion of tagged 1,1-diphenyl ethane); in a triblock SBR copolymer cast from different solvents and also molded at elevated temperature; and in cis-polybutadiene filled to different extents with carbon black, calcium carbonate, and microglass spheres. The diffusion coefficient in random SBR copolymers decreased with increasing content of styrene and/or vinyl configuration and could be correlated with fractional free volume on the basis of linear additivity of the cis, trans, vinyl, and styrene moieties. In SBR block copolymers, the diffusion coefficient increased with increasing average block sequence length. For the triblock copolymer, the diffusion coefficient was approximately the same for samples molded or cast from solvents which are good for polybutadiene, but was far smaller for a sample cast from ethyl acetate, in which the polystyrene domains are probably lamellar. The effect of fillers on diffusion in cis-polybutadiene was compared with calculations on the basis of several theoretical models.     

Heat capacity of random copolymers of styrene and methacrylates

Differential scanning calorimetry has been used to investigate the thermal behavior of random copolymers of styrene and hexyl methacrylate and of styrene and glycidyl methacrylate in the temperature range of 20° to 150°C. Heat capacities of the copolymers and homopolymers, poly-(hexyl methacrylate), poly(glycidyl methacrylate), and polystyrene have been measured. It is found that the heat capacities of the homopolymers from 60°K to the glass transition temperatures can be adequately obtained by Wunderlich's empirical method. It is also found that the copolymer heat capacities can be adequately represented by addition of homopolymer heat capacities.     

Preparation of block copolymers of styrene and methacrylic acid

A range of block copolymers of styrene and methacrylic acid has been prepared by the suspension method involving migration of a growing radical across a phase boundary. The way in which copolymer composition varies with change in the amount of the two monomers in the reaction mixture has been studied, and explanations are suggested to account for these variations. Two methods, involving calculation from solubility data and thermogravimetric analysis respectively, have been used to give an estimate of the length and composition of the blocks.     

丁苯嵌段共聚物的催化氢化研究进展

介绍了丁苯嵌段共聚物的催化加氢技术，综述了茂金属催化剂，环烷酸镍（钴）催化剂，三苯基膦-氯化钌（铑），铁钴镍螯合物均相催化剂及非均相催化剂的技术进展。讨论了氢化丁苯嵌段共聚物氢化度的定性分析和定量分析方法。