Effect of Temperature on Ozone Cracking of Rubbers

1966 ◽  
Vol 39 (3) ◽  
pp. 643-650
Author(s):  
A. N. Gent ◽  
J. E. McGrath
Keyword(s):  
Polymer Chains ◽  
Effect Of Temperature ◽  
Ozone Molecule ◽  
Segmental Mobility ◽  
Network Chain ◽  
Styrene Copolymers ◽  
Rates Of Growth ◽  
Rate Controlling Step ◽  
Limiting Value ◽  
Butadiene Styrene

Abstract The rates of growth of single ozone cracks have been measured for vulcanizates of a series of butadiene—styrene copolymers, over a temperature range from − 5° C to 95° C. The rates appear to be determined by two mechanisms. At low temperatures, near the glass transition temperature, they are quantitatively related to the segmental mobility of the polymer. The principal rate-controlling step in this case is concluded to be movement of the polymer chains after scission to yield new surface. At high temperatures the rate approaches a limiting value of 10−3 cm/sec/mg of ozone/1. This is about 1/1000 of the maximum possible value when instantaneous reaction of one incident ozone molecule causes scission of one network chain.

Effect of Temperature on Ozone Cracking of Butyl Rubbers

1968 ◽  
Vol 41 (5) ◽  
pp. 1294-1299 ◽  
Author(s):  
A. N. Gent ◽  
H. Hirakawa
Keyword(s):  
Crack Growth ◽  
Ozone Concentration ◽  
Effect Of Temperature ◽  
Segmental Mobility ◽  
Temperature Range ◽  
Styrene Copolymers ◽  
The Difference ◽  
Rates Of Growth ◽  
Rate Controlling Step ◽  
Butadiene Styrene

Abstract Rates of growth of single ozone cracks have been measured for vulcanizates of two butyl rubbers over the temperature range of 20-160° C. Over most of this range the rates are quantitatively related to the segmental mobility of the polymer and depend upon temperature in accord with the appropriate form of the WLF relation. The rates are also proportional to the concentration of ozone. It is therefore concluded that diffusion of ozone into the polymer before reaction is the rate-controlling step. This is contrasted with the behavior of butadiene styrene copolymers, for which rates of crack growth are also quantitatively related to the segmental mobility, but the rates are somewhat larger at equivalent mobilities and the dependence upon ozone concentration is smaller. The difference is attributed to different penetration distances before reaction in polymers containing low and high densities of reactive sites.

Properties of Random and Block Copolymers of Butadiene and Styrene. III. Three Sequence Styrene-Butadiene-Styrene Block Polymers

1967 ◽  
Vol 40 (4) ◽  
pp. 1183-1199 ◽  
Author(s):  
C. W. Childers ◽  
G. Kraus
Keyword(s):  
Tensile Strength ◽  
Block Copolymers ◽  
Polymer Chains ◽  
Two Phase ◽  
Styrene Copolymers ◽  
Relaxation Measurements ◽  
Styrene Butadiene Styrene ◽  
Increasing Temperature ◽  
Styrene Butadiene ◽  
Butadiene Styrene

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.

Properties of Ebonite. XXXVII. Electrical Properties of Synthetic Rubber Ebonites

1949 ◽  
Vol 22 (4) ◽  
pp. 1084-1091
Author(s):  
D. G. Fisher ◽  
L. Mullins ◽  
J. R. Scott
Keyword(s):  
Natural Rubber ◽  
Power Factor ◽  
Power Loss ◽  
Ionic Conduction ◽  
Effect Of Temperature ◽  
Plastic Yield ◽  
Styrene Copolymers ◽  
Synthetic Rubber ◽  
High Dielectric ◽  
Butadiene Styrene

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.

Effect of the Temperature of Polymerization on the Structure of Butadiene-Styrene Copolymers

1956 ◽  
Vol 29 (2) ◽  
pp. 419-422 ◽  
Author(s):  
A. P. Sheĭnker ◽  
S. S. Medvedev
Keyword(s):  
Polymer Chain ◽  
Polymer Chains ◽  
Structural Variations ◽  
Dilatometric Method ◽  
Styrene Copolymers ◽  
Magnetic Stirrer ◽  
Different Temperatures ◽  
Infrared Spectrometer ◽  
The Subject ◽  
Butadiene Styrene

Abstract The addition of monomer molecules to the growing polymer chain during the polymerization of dienes may take place in several ways. In the polymerization of butadiene, the addition takes place in the 1,2- and 1,4-positions. In the latter case polymer chains are obtained with structural variations, e.g., the position of CH2 groups at the double bonds is cis or trans. The resulting polymer chains vary in configuration. It is of interest to determine how the configuration is affected by different conditions of polymerization. Several papers related to the subject are to be found in the literature. In this work, we studied with an infrared spectrometer the compositions of butadiene-styrene copolymers prepared at different temperatures. Also determined was the content of the various configurations of butadiene links in the polymer chains. The samples were prepared by polymerizing emulsions by the dilatometric method in the absence of oxygen. A satisfactory emulsion was obtained with a magnetic stirrer inserted into the dilatometer (Figure 1 ). The rotation of the stirrer (activated by a magnet attached to the axis of a motor under the thermostat) sucked the upper part of the liquid through the upper opening (1) and expelled it through the side opening (2); this assured emulsification.

X-Ray Studies of Low-Temperature Polybutadiene and Butadiene-Styrene Copolymers

1949 ◽  
Vol 22 (2) ◽  
pp. 356-369 ◽  
Author(s):  
Karl E. Beu ◽  
W. B. Reynolds ◽  
C. F. Fryling ◽  
H. L. McMurry
Keyword(s):  
Molecular Weight ◽  
Low Temperature ◽  
Polymer Chains ◽  
Polymerization Temperature ◽  
X Ray ◽  
Styrene Copolymers ◽  
Emulsion Polymerizations ◽  
Diffraction Patterns ◽  
Ray Patterns ◽  
Butadiene Styrene

Abstract Although it is now generally recognized that the temperature of polymerization affects profoundly the properties of emulsion elastomers, there is very little evidence available pertaining to the cause of the variations of properties. It is felt by some that the improved properties of low-temperature elastomers can be related to variations in molecular weight and molecular-weight distribution. In this laboratory, however, the opinion has prevailed that the lower emulsion polymerization temperatures appreciably alter the fine structure of the molecules with an increase in the regularity of the polymer chains. If there were actually less branching and cross-linking in low-temperature polymers, and less 1,2-addition to monomer components, the increased order should be evident from x-ray diffraction patterns. To provide information on the above questions, x-ray studies were made with four purposes in view: (1) to determine the effect of polymerization temperature on the crystallization properties of unstretched and stretched polybutadienes; (2) to determine the influence of styrene content on the crystallization of butadiene-styrene copolymers; (3) to study some effects of compounding and vulcanization on crystallizable polybutadiene; and (4) to use the preferred orientation patterns obtained from some of these polymers for structural evaluations. To accomplish these objectives, x-ray patterns were obtained at several temperatures of some unstretched and stretched polybutadiene polymers, butadiene-styrene copolymers, and a vulcanized and compounded polybutadiene. The polybutadienes were prepared by emulsion polymerizations at 55°, 40°, 30°, 20°, 5°, −10° and −20° C. Since the −20° C polybutadiene showed the most marked crystallization patterns, the effects of compounding and of styrene addition were studied, using polymers prepared at this temperature for comparison. Three butadiene-styrene copolymers containing, respectively, 10, 20, and 30 per cent styrene in the monomer charge and one vulcanized polybutadiene compounded with Wyex carbon black were studied.

Chemical Stress Relaxation of NR Networks Prepared in the Swollen State

1986 ◽  
Vol 59 (4) ◽  
pp. 541-550 ◽  
Author(s):  
Kyung-Do Suh ◽  
Hidetoshi Oikawa ◽  
Kenkichi Murakami
Keyword(s):  
Stress Relaxation ◽  
Network Structure ◽  
Three Dimensional ◽  
Polymer Chains ◽  
Chemical Stress ◽  
Network Chain ◽  
Crosslinking Process ◽  
Dimensional Network ◽  
Chemical Relaxation ◽  
The Difference

Abstract From the experimental results of the present investigation, it is apparent that two kinds of networks which have a different three-dimensional network structure give quite different behavior of chemical stress relaxation, even if both networks have the same network chain density. The difference in three-dimensional network structure for the two kinds of rubber arises from the degree of entanglement, which changes with the concentration of the polymer chains prior to the crosslinking process. The direct cause of chemical relaxation is due to the scission of network chains by degradation, whereas the total relaxation is caused by the change of geometrical conformation of network chains. This then casts doubt on the basic concept of chemorheology which is represented by Equation 2.

scholarly journals Glass Transition and Interfacial Segmental Dynamics in Polymer-Particle Composites

2008 ◽  
Vol 81 (3) ◽  
pp. 506-522 ◽  
Author(s):  
C. G. Robertson ◽  
C. M. Roland
Keyword(s):  
Glass Transition ◽  
Relaxation Times ◽  
Polymer Particle ◽  
Polymer Chains ◽  
Nano Particle ◽  
Segmental Mobility ◽  
Segmental Dynamics ◽  
Reinforcing Fillers ◽  
Segmental Relaxation ◽  
Polymer Interaction

Abstract We review the literature concerned with the effect of proximity to a filler surface on the local segmental mobility of polymer chains. This mobility is commonly assessed from either the glass transition temperature, Tg, or the segmental relaxation times measured by mechanical, dielectric, or NMR spectroscopy. Published studies report increases, decreases, or no change in Tg upon the addition of carbon black, silica, and other reinforcing fillers. Similarly, the segmental relaxation times have been found to increase or be invariant to the presence of nanometer-sized particles. Some of these discrepancies can be ascribed to ambiguous methods of data analysis; others likely reflect the variation in filler-polymer interaction among different systems. There are unequivocal examples of polymers that have segmental dynamics and glass transitions unaffected by nano-particle reinforcement. However, the general principles governing the behavior remain to be clarified, with further work, focusing on the micromechanics at the particle interface, required for resolution of this important aspect of rubber science and technology.

Thermal Analysis of Butadiene Styrene Block Copolymers

1969 ◽  
Vol 42 (3) ◽  
pp. 918-923 ◽  
Author(s):  
J. N. Anderson ◽  
F. C. Weissert ◽  
C. J. Hunter
Keyword(s):  
Thermal Analysis ◽  
Osmium Tetroxide ◽  
Polymer Degradation ◽  
Glass Temperature ◽  
Index Method ◽  
K Value ◽  
Styrene Copolymers ◽  
Compositional Distribution ◽  
Composition Graph ◽  
Butadiene Styrene

Abstract The Gordon—Taylor—Wood relationship between composition and glass temperature has been used as the basis of a DTA method for block styrene analysis in butadiene styrene copolymers having the same microstructure and a similar compositional distribution. The determined K value of the Gordon—Taylor—Wood equation for these polymers prepared with a butyllithium catalyst is in fair agreement with values previously determined for emulsion butadiene styrene copolymers. The total styrene content of the copolymer was determined using the refractive index method, and the composition of the “non-block” segment of the copolymer was obtained from DTA measurement using a Tg as a function of composition graph The amount of block styrene can then be obtained by difference. Evidence is presented supporting the validity of the method, and the results are compared with those obtained by a chemical method which involved polymer degradation by a hydroperoxide in the presence of osmium tetroxide. The thermal analysis requires approximately one-half hour. All measurements are made on the dry polymer eliminating the necessity of redissolving the polymer as required by most other methods of analysis.

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