Butadiene-Styrene Resinous Copolymers

1951 ◽  
Vol 24 (3) ◽  
pp. 697-708
Author(s):  
J. D. D'Ianni ◽  
L. D. Hess ◽  
W. C. Mast

Abstract Although high-styrene resins have become of great commercial importance during the past 5 years (approximately 25,000,000 pounds manufactured in 1949), comparatively little information on the polymerization processes or any systematic review of their properties can be found in the technical literature. The object of the present paper is to supply such information. A series of butadiene-styrene copolymers with charging ratios of 50/50, 40/60, 30/70, 20/80, and 10/90 was prepared. Polystyrene, prepared under the same conditions, was included as a control. Properties of the latexes and resins obtained, presented in a systematic manner, were found to be largely dependent on the monomer ratio employed in the polymerization. for the first time a coherent picture is presented of the entire plastic range of the styrene-butadiene resins. This should encourage the further development of this large and expanding field, which includes such applications as natural and synthetic rubber reinforcing, impact resistant compositions, protective coatings, and latex paints.

1967 ◽  
Vol 40 (4) ◽  
pp. 1183-1199 ◽  
Author(s):  
C. W. Childers ◽  
G. Kraus

Abstract In butadiene styrene copolymers containing long block sequences chain segments associate with like segments to form a two phase structure. Properties of such polymers are dependent not only on composition and molecular weight but also on block sequence along the chain. Polymers containing two or more polystyrene blocks per molecule form networks and exhibit elastomeric properties in the uncured state resembling those of filler reinforced vulcanizates. This behavior is shown both by linear styrene-butadiene-styrene elastomers and multichain block copolymers branched in the polybutadiene blocks. A prominent loss tangent peak was observed around —40° C for the multichain polymers. Stress strain following prestretching and stress relaxation measurements indicate some shifting of polystyrene associations during stretching. Tensile strength is reduced by increasing temperature and addition of plasticizers. Reinforcement by polystyrene domains in vulcanized block copolymers is evident from tensile strength, dynamic modulus, and swelling measurements, but decreases with increased crosslinking. The number of styrene sequences in the primary molecules is less important after vulcanization as crosslinking destroys the individuality of the original polymer chains.


1949 ◽  
Vol 22 (4) ◽  
pp. 1084-1091
Author(s):  
D. G. Fisher ◽  
L. Mullins ◽  
J. R. Scott

Abstract Experiments were carried out to explore the possibility of making good electrical ebonites from various types of synthetic rubber. The ebonites produced were tested for permittivity and power factor over wide ranges of temperature and frequency. Thioplasts (Thiokols AZ and FA) apparently do not produce hard ebonitelike vulcanizates by the normal procedure. Neoprenes (GN and I) give ebonites, but with such high dielectric power loss as to be unsuitable for use as high-frequency dielectrics; moreover, if the mix contains zinc oxide, the ebonite has a very hygroscopic and therefore electrically unsatisfactory surface. Butadiene copolymers containing polar groups (butadiene-acrylonitrile types and Thiokol RD) give ebonites with high power loss, hence are not suitable for making high-grade electrical ebonites. Polybutadiene (Buna-85) and butadiene-styrene copolymers (GR-S, Hycar-EP, Buna-S) are much nearer to natural rubber as far as the radio-frequency (100 to 2,500 kc. per sec.) power loss of their ebonites is concerned. The GR-S ebonite examined was not so good as natural rubber at room temperature, but was superior above about 50° C. Buna-85 and Hycar-EP were superior to natural rubber over the whole temperature range; indeed, the high-styrene copolymers, as represented by Hycar-EP and Buna-SS, appear to be the best type of synthetic rubber for making ebonite with low power loss, especially at high frequencies and temperatures. The effects of changing temperature and frequency on permittivity and power factor are discussed. Attention is drawn to the big effect of temperature on power factor; this was less with polybutadiene and butadiene-styrene ebonites than with natural rubber ebonite, in keeping with the greater heat resistance of the former as judged by plastic yield tests. Comparison of the effects of rising temperature and decreasing frequency shows that these produce broadly similar effects on power factor, as would be expected on theoretical grounds, but that rising temperature superposes a second effect (an increase), presumably due to increased ionic conduction.


1947 ◽  
Vol 20 (1) ◽  
pp. 241-248
Author(s):  
A. M. Borders ◽  
R. D. Juve ◽  
L. D. Hess

Abstract Early in the investigation of butadiene-styrene copolymers as synthetic rubbers, this laboratory became interested in copolymers containing much more styrene than any of the American or German synthetics. This interest was soon directed to the resinous copolymers obtained when the styrene content is increased beyond the range in which rubberlike properties are observed at room temperature. The exploratory work, therefore, involved preparation and evaluation of butadiene-styrene copolymers containing from 65 to 98 per cent styrene. No description of similar polymers has been found. Konrad and Ludwig claimed the improvement of rubberlike properties of butadiene-styrene copolymers by increasing the styrene content from the normal range to “between about 47.5 and about 70 per cent”. The claims and examples of this patent emphasize the improvement of rubberlike properties, such as tensile, elongation, and rebound, at high temperatures. It is well known in this country, however, that increase in styrene content beyond a certain point, perhaps 50–55 per cent, is accompanied by a loss of overall balance of rubber characteristics. Therefore, the copolymers at the upper end of the range described by Konrad and Ludwig have definite limitations for rubber uses—for example, low rebound, high brittle point, shortness, etc. In the writers' laboratory useful resins have been prepared from dienes and vinyl aryl hydrocarbons in the range 5 to 20 per cent diene and 80 to 95 per cent vinyl aryl hydrocarbon. This paper describes the properties and certain uses of one of these copolymers containing approximately 15 parts of butadiene and 85 parts of styrene. This material possesses a combination of physical and chemical properties which permit its use in several applications where cyclized natural or synthetic rubbers are commonly employed. Cyclized natural rubber has been described by Bruson, Endres, and Thies and Clifford. Cyclized synthetic rubbers were described recently by Endres. One product of this type is made from a special synthetic rubber. The new 15 butadiene—85 styrene copolymer is now identified as Pliolite S-3, since it may be used in many Pliolite applications, often with distinct advantages over either the natural or synthetic rubber derivatives.


1959 ◽  
Vol 32 (1) ◽  
pp. 321-327 ◽  
Author(s):  
B. A. Dolgoplosk ◽  
E. I. Tinyakova ◽  
V. N. Reĭkh ◽  
T. G. Zhuravleva ◽  
G. P. Belonovskaya

Abstract It is well known that the high strength of unfilled (pure gum) natural rubber and some synthetic rubber compounds can be explained by the homogeneity of the polymer chain which determines its ability to crystallize or to orient on stretching. The character of the vulcanization network as well as the structure of the main chain is of importance. This has been verified by the use of polyethylene polyamines and other chemical compounds as vulcanization accelerators for butadiene-styrene rubber (SKS-30A) to produce high strength (up to 200 kg/cm2) gum rubber compounds. In certain cases, only the structure of the vulcanization network obtained with carboxyl-containing rubber compounds can account for obtaining the same effects as are obtained with natural or other synthetic rubber compounds as a result of homogeneity of polymer chain. The first work done by us on carboxyl-containing (carboxylic) rubbers was done in 1954\2-1955. In this work it was shown that polymers of isoprene and of butadiene, copolymers of butadiene with styrene, butadiene with acrylonitrile, and others, which contain small quantities of methacrylic acid (1\2-2 mole %) in the chain, can be vulcanized with oxides of divalent metals to give pure gum and lightly filled compounds characterized by high strength and elasticity, good resistance to heat aging and good cut growth resistance.


1950 ◽  
Vol 23 (4) ◽  
pp. 760-769
Author(s):  
R. D. Juve ◽  
J. W. Marsh

Abstract Synthetic rubbers and natural rubber increase in stiffness at low temperatures and tend to lose their elastic characteristics. This stiffening and hardening phenomenon occurs in varying degrees with various elastomers. Natural rubber and certain synthetic rubbers crystallize during extended exposure at low temperature, whereas other synthetic rubbers such as GR-S remain amorphous. In a general review of the low temperature properties of synthetic rubber, Liska has shown that decreased styrene in butadiene-styrene copolymers improves the flexibility at low temperature. The low temperature flexibility of vulcanized articles made from any particular rubber or synthetic rubber is influenced by the compounding ingredients admixed with the elastomer. This paper shows the results of some studies of the effect of these compounding ingredients on the low temperature serviceability of butadiene-styrene copolymers. Somewhat similar work on the effect of a large number of plasticizers in GR-S has been conducted at the Rubber Laboratory, Mare Island Naval Shipyard, with particular emphasis on compression set at low temperature.


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