Physical Properties of Diene Polymers. Effects of Side Vinyl Groups and Other Structural Features

1948 ◽  
Vol 21 (3) ◽  
pp. 596-604
Author(s):  
James D. D'Ianni
Keyword(s):  
Tensile Strength ◽  
Natural Rubber ◽  
Physical Properties ◽  
Molecular Structures ◽  
Acid Oxidation ◽  
Similar Data ◽  
Molecular Weight Range ◽  
Brittle Point ◽  
Organometallic Catalyst ◽  
Butadiene Styrene

Abstract The detailed molecular structures of natural rubber, emulsion polyisoprene, polyisoprene prepared with an organometallic catalyst, and sodium polyisoprene were studied by comparison of data available from infrared absorption spectra, perbenzoic acid titration, refractive index, density, iodine number, chromic acid oxidation, and hydrochlorination. These polymers showed decreasing amounts of 1,4-addition content in the order listed. Similar data were collected where possible for emulsion polybutadiene, polybutadiene prepared with an organometallic catalyst, and potassium polybutadiene (Buna-85), as well as for GR-S and corresponding butadiene-styrene copolymers prepared with an organometallic catalyst and with sodium. These two groups also showed decreasing 1,4-addition content in the order listed. Correlation of structure inferred from the above data with physical properties of corresponding tread stock vulcanizates indicated that for diene polymers with decreasing amount of 1,4-addition content the brittle point rose, the rebound value decreased, and the tensile strength increased, provided comparison was restricted to polymers of approximately the same molecular weight range made with the same monomer. Natural rubber occupied a unique position because it was substantially a linear high polymer with the cis-configuration around all the double bonds. For the butadiene-styrene 75/25 copolymers the brittle point rose with decreasing amount of 1,4-addition content, but no satisfactory correlation could be obtained for the tensile strength and the rebound value, probably because of the predominant effect of the phenyl side groups.

Polybutadienes of Controlled Cis, Trans and Vinyl Structures

1959 ◽  
Vol 32 (2) ◽  
pp. 614-627 ◽  
Author(s):  
J. N. Short ◽  
G. Kraus ◽  
R. P. Zelinski ◽  
F. E. Naylor
Keyword(s):  
Tensile Strength ◽  
Low Temperature ◽  
Natural Rubber ◽  
Physical Properties ◽  
Abrasion Resistance ◽  
High Hardness ◽  
High Modulus ◽  
High Tensile Strength ◽  
Truck Tires ◽  
Wide Range

Abstract The physical properties of polybutadiene vulcanizates have been measured as a function of polymer microstructure. Although the over-all properties of any one polybutadiene are determined by the relative ratio of cis, trans and vinyl units in the polymer chain, marked changes in physical properties do not occur until a relatively pure configuration is approached or unless the raw polymer displays crystallinity. Thus, polybutadienes containing more than 85 per cent cis, trans or vinyl units are characteristically different from each other and the differences are accentuated as the isomeric forms approach 100 per cent of a given configuration. Polybutadiene of 95 per cent cis configuration displays very low heat generation and high resilience (equaling natural rubber in these properties) and excellent abrasion resistance. trans-Polybutadiene (90 per cent), a crystalline plastic in the raw state, becomes rubbery after vulcanization. Gum vulcanizates possess high tensile strength, and tread stocks display high modulus and tensile strength, high hardness and fair hysteresis properties. Vulcanizates of amorphous 94 per cent vinyl polybutadiene are characterized by fair tensile properties, low hysteresis, and poor low temperature properties. Crystalline syndiotactic polybutadiene, 70 per cent vinly, displays much higher gum and tread tensile strengths than its amorphous counterpart. Amorphous polybutadienes containing less than 70–80 per cent of any one configuration are generally similar in most properties, and resemble emulsion polybutadiene in many respects. The wide range of properties of the various polybutadienes makes them suitable for many applications. cis-Polybutadiene is an excellent tire rubber, which has given as much as 40 per cent greater abrasion resistance than natural rubber in passenger tire tests. Heavy duty 10:00 × 20 truck tires fabricated with a 1:1 blend of cis-polybutadiene and natural rubber in the treads have given slightly better abrasion ratings and lower running temperatures than control tires fabricated entirely from natural rubber. Amorphous 80 per cent cis-polybutadiene has been found to possess exceptionally good low temperature properties, far superior to present arctic-type unsaturated elastomers, trans-Polybutadienes by virtue of their high modulus, high tensile strength, and high hardness could be utilized in the preparation of hard rubber goods, floor tiles, and shoe soles. While none of these polybutadienes is yet available commercially, their unusual properties and potential applicability in many areas should lead to their manufacture in the future.

Effect of Carbon Black on Curing Behavior, Mechanical Properties and Viscoelastic Behavior of Natural Sponge Rubber-Based Nano-Composites

2012 ◽  
Vol 510-511 ◽  
pp. 532-539 ◽  
Author(s):  
M.A. Bashir ◽  
M. Shahid ◽  
R.A. Alvi ◽  
A.G. Yahya
Keyword(s):  
Mechanical Properties ◽  
Tensile Strength ◽  
Carbon Black ◽  
Natural Rubber ◽  
Physical Properties ◽  
Viscoelastic Behavior ◽  
Nano Composites ◽  
Curing Behavior ◽  
Auxetic Materials ◽  
Viscosity Variation

Natural rubber (polymer designation cis-1-4 polyisoprene, is obtained from the sap ("latex") of several rubber-yielding plants (e.g.,HeveaBrasiliensisandPartheniaargentatum) by coagulation with chemicals, drying, electrical coagulation, and other processes. Foamy or sponge structure of natural rubber (NR) is very useful in aerospace and as auxetic materials (exhibiting negative poisons ratio) for use in application of homeland security.The main aim of this research to estimate the influence of carbon black on mechanical properties, curing and viscosity variation behaviors of the natural rubber based composites. Different amounts of carbon black were used along with other fillers. The influence of carbon black on curing behavior and mechanicalproperties of natural rubber foams was investigated at different feedingratios of the carbon black. The physical properties of the foamed NRs were then measured as a function of carbon blacks content. The mechanical properties of the foamed NRs such as tensile strength,strength at break and modulus,were gradually increased with increasingcarbon black content whereas elongation decreasedat break.

Studies of the Vulcanization of Rubber. III. Kinetics of Change of Tensile Strength of Natural Rubber during Vulcanization

1954 ◽  
Vol 27 (3) ◽  
pp. 615-621 ◽  
Author(s):  
B. Dogadkin ◽  
B. Karmin ◽  
I. Golberg
Keyword(s):  
Molecular Weight ◽  
Tensile Strength ◽  
Natural Rubber ◽  
Structure Formation ◽  
Linear Function ◽  
General Equation ◽  
Original Material ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Butadiene Styrene

Abstract 1. It is shown that the tensile strength of vulcanized butadiene-styrene rubber is a linear function of the plasticity of the original material. 2. Proceeding from concepts of the presence during vulcanization of a number of opposing processes of structure formation and destruction, both of which influence the molecular weight of the rubber, a general equation is derived which expresses the kinetics of the change of tensile strength of a vulcanizate. 3. Experimental material is offered which proves the applicability of the proposed equation to the representation of the kinetics of vulcanization of mixtures of natural rubber containing relatively small sulfur contents, i.e., up to 3 per cent.

Study of Cure Synergism of the Thiocarbamylsulfenamide-Dibenzothiazyl Disulfide Accelerator System in the Vulcanization of Natural Rubber

1983 ◽  
Vol 56 (4) ◽  
pp. 827-837 ◽  
Author(s):  
D. Pal ◽  
B. Adhikari ◽  
D. K. Basu ◽  
A. K. Chaudhuri
Keyword(s):  
Tensile Strength ◽  
Natural Rubber ◽  
Physical Properties ◽  
Structural Characterization ◽  
Crosslink Density ◽  
Synergistic Activity ◽  
Elongation At Break ◽  
Equimolar Concentration ◽  
Accelerator System

Abstract N-cyclopentamethylenethiocarbamyl-N′-cyclopentamethylenesulfenamide (CPTCS) and dibenzothiazyldisulfide (MBTS), as binary accelerators in a mixture have been found to provide significant mutual enhanced activity with regard to modulus, tensile strength, hardness, and elongation at break in the vulcanization of NR gum stocks. The synergistic activity of the CPTCS-MBTS system is very much dependent upon the accelerator ratios, concentration of sulfur and accelerator, as well as the temperature of vulcanization. Investigations carried out with the Monsanto rheometer also corroborate the above results. It is suggested that the synergism arises out of the interaction between CPTCS and MBTS which produces intermediate accelerators. N,N-Diethylthiocarbamyl-N′-cyclohexylsulfenamide (DETCS) in conjunction with MBTS, produces similar results in the vulcanization of NR. Structural characterization of the vulcanizates obtained at 140 and 160°C reveals that predominantly monosulfidic linkages are obtained with CPTCS or DETCS and MBTS combinations. The intermediate combinations, at near equimolar concentration of the two accelerators, exhibit maximum crosslink density. An attempt has been made to correlate physical properties with crosslink density as well as various types of crosslinks.

Property Enhancement of Silica-Filled Natural Rubber Compatibilized with Epoxidized Low Molecular Weight Rubber by Extra Sulfur

2013 ◽  
Vol 844 ◽  
pp. 235-238 ◽  
Author(s):  
Prachid Saramolee ◽  
Kannika Sahakaro ◽  
Natinee Lopattananon ◽  
Wilma Dierkes ◽  
Jacques W.M. Noordermeer
Keyword(s):  
Molecular Weight ◽  
Tensile Strength ◽  
Natural Rubber ◽  
Network Formation ◽  
Periodic Acid ◽  
Low Molecular Weight ◽  
Molecular Weight Range ◽  
Small Influence ◽  
Silane Molecule ◽  
Mooney Viscosity

The properties of both compounds and vulcanizates of silica-filled natural rubber (NR) compatibilized with epoxidized low molecular weight natural rubbers (ELMWNRs) consisting of 12 and 28 mol% epoxide are investigated. The ELMWNRs with a molecular weight range of 50,000 to 60,000 g/mol are produced by depolymerization of epoxidized natural rubber (ENR) latex using periodic acid, and then used as compatibilizer in a range of 0 to 15 phr in virgin NR. The compounds with LMWNR without epoxide groups, and with bis-(triethoxysilylpropyl) tetrasulfide (TESPT) coupling agent are also prepared for comparison purpose. Incorporation of ELMWNRs lowers Mooney viscosity and Payne effect to the level closed to that of silica/TESPT compound, and clearly enhances the modulus and tensile strength of vulcanizates compared to the compounds with no compatibilizer and LMWNR. The higher epoxide groups content results in the better tensile properties but somewhat less than the compound with TESPT. Addition of extra sulfur into the compounds with LMWNR and ELMWNRs to compensate for the sulfur released from silane molecule in the silica/TESPT system shows small influence on Mooney viscosity, but remarkably enhances 300% modulus, tensile strength and loss tangent at 60°C as a result of the better network formation.

Rupture of Rubber. IV. Tear Properties of Vulcanizates Containing Carbon Black

1957 ◽  
Vol 30 (2) ◽  
pp. 584-595
Author(s):  
H. W. Greensmith
Keyword(s):  
Tensile Strength ◽  
Carbon Black ◽  
Natural Rubber ◽  
Physical Properties ◽  
Different Types ◽  
Tear Properties

Abstract A method of studying tear behavior has been described in a previous paper (Part III, subsequently referred to as III), and was illustrated by results obtained with natural rubber and GR-S gum vulcanizates, i.e., vulcanizates containing no added ingredients apart from those necessary for vulcanization. In the present paper the method is applied to vulcanizates containing different types of carbon black. Vulcanizates of this type are of considerable interest, since the carbon black can appreciably modify physical properties such as stiffness and tensile strength and can induce pronounced anisotropy in tearing, referred to by Buist as knotty tearing.

Control of Mechanical Properties and Permeability of Electrospun Natural Rubber with Different Composite Systems

2010 ◽  
Vol 93-94 ◽  
pp. 619-622 ◽  
Author(s):  
Sarawuth Sithornkul ◽  
Poonsub Threepopnatkul
Keyword(s):  
Mechanical Properties ◽  
Tensile Strength ◽  
Natural Rubber ◽  
Testing Machine ◽  
Acrylonitrile Butadiene Styrene ◽  
Optimum Conditions ◽  
Fiber Mats ◽  
Vapour Permeability ◽  
Composite Systems ◽  
Butadiene Styrene

The electrospun natural rubber (NR) with two different components namely: acrylonitrile butadiene styrene (ABS) and carbon black (CB) have been extensively studied. The main objective was to investigate the mechanical properties and permeability dependency of NR/ABS and NR/CB as well as its contents. NR/CB was compounded by torque rheometer (Brabender) while ABS was dissolved with NR using tetrahydrofuran (THF) as its solvent. Sulfur was used as the vulcanizing agent in both systems. Mechanical properties were evaluated by universal testing machine and permeability was observed by water vapour permeability. The optimum conditions for electrospun NR/ABS and NR/CB non-woven mats were as follows: flow rate 30 ml/h, voltage 15 kV, collector distance 20 cm and collected on rotating circular plate at 1000 rpm. The results of mechanical properties showed that for electrospun NR/CB fiber membranes, the higher the CB loading it had, the lower its tensile strength and elongation it would be. Whilst electrospun NR/ABS fiber mats, the elongation behavior was affected by the ABS loading but not the tensile strength. For permeability, NR/CB was shown to possess relatively higher permeability than the NR/ABS non-woven mats.

Effect of Cis-Trans Ratio on the Physical Properties of 1,4 Polybutadienes

1957 ◽  
Vol 30 (4) ◽  
pp. 1118-1141 ◽  
Author(s):  
J. N. Short ◽  
V. Thornton ◽  
G. Kraus
Keyword(s):  
Tensile Strength ◽  
Carbon Black ◽  
Physical Properties ◽  
Low Temperatures ◽  
Elevated Temperatures ◽  
Trans Content ◽  
Wide Range ◽  
Brittle Point ◽  
Low Sulfur ◽  
In Cis

Abstract The physical properties of vulcanized 1,4 polybutadienes, prepared by heterogeneous catalysis and ranging from 95 per cent cis to nearly 100 per cent trans configuration, were investigated in gum and tread formulations. Comparisons were made at equal effective (physical) degree of crosslinking for both gum- and carbon black-reinforced stocks and for black stocks at equal 300 per cent modulus. In general, as polybutadienes require less sulfur for adequate vulcanization than trans polybutadienes. Vulcanizates of all 1,4 polybutadienes exceeding 15 per cent in cis content are completely rubbery at ordinary temperatures. Polybutadiene of 93 per cent trans content yields tough, leathery, crystalline vulcanizates at 80° F, which become rubbery at moderately elevated temperatures. Without exception the important physical properties change little between 25 and 80 per cent cis content. At both ends of this range the tensile strength of both gum and black stocks rises as a consequence of increasing chain regularity. However, in gum tensile strength not even the highest cis polybutadienes are equivalent to natural or synthetic cis-polyisoprenes. Black stocks of very good tensile strength with elongations ranging from 500 to 700 per cent are obtained with both cis- and trans-polybutadienes. At the crosslinking level for optimum tensile strength, modulus increases with trans content. The cis-polybutadienes have excellent resilience and low hysteresis and maintain their resilience to temperatures as low as −40° F. The latter is true even of the highest as polymers which crystallize at these temperatures. The tendency to crystallize rapidly at low temperatures disappears between 87 and 82 per cent cis content so that polymers of moderately high cis unsaturation have exceptional low-temperature characteristics. These polymers remain completely rubbery down to their brittle point (ca. −85° C). The excellent resilience of cis-polybutadiene is particularly apparent in carbon black-reinforced stocks. Because of the inherently low modulus of these stocks and their low sulfur requirement, these may be vulcanized to rather high degrees of crosslinking. This results in further improvements in resilience and heat build-up with only moderate sacrifices in tensile strength and ultimate elongation. Vulcanizates of 70 to 80 per cent trans-polybutadienes exhibit evidence of crystallinity over a wide range of temperatures and are probably not completely melted at room temperature. Although their resilience is less than that of the high cis-polybutadienes, it is still somewhat better than that of SBR, particularly at low temperatures. The 1,4 polybutadienes are more resistant to oxidative scission than emulsion polybutadiene or SBR and are greatly superior to natural rubber in this respect. The dominant effect in the aging of 1,4 polybutadienes is crosslinking. Because of their low sulfur requirements the cis polybutadienes offer a particular advantage in aging resistance. None of the polybutadienes exhibits ozone resistance comparable to Hevea.

Oxidation of GR-S and Other Elastomers

1947 ◽  
Vol 20 (3) ◽  
pp. 747-759
Author(s):  
John O. Cole ◽  
James E. Field
Keyword(s):  
Tensile Strength ◽  
Natural Rubber ◽  
Physical Properties ◽  
Experimental Methods ◽  
Chain Scission ◽  
Cross Linking ◽  
Antioxidant Action ◽  
Mechanism Of Oxidation ◽  
Natural Rubber Vulcanizates

Abstract The effect of heat aging on the physical properties of an elastomer is generally considered the result of oxidation, which produces both chain scission and cross-linking in the polymer. Early in the development of GR-S, a marked difference in the aging of GR-S and natural rubber vulcanizates was observed. From the effect of aging on hardness, tensile strength, modulus, and elongation it appeared that cross-linking occurred more rapidly than chain scission with GR-S, but the reverse was true with natural rubber. The work reported here was undertaken to provide a better understanding of the differences in aging of GR-S and natural rubber and to introduce new experimental methods for studying the mechanism of oxidation and antioxidant action in elastomers.

Structural Features of Buna-S. Relation to Physical Properties

1945 ◽  
Vol 18 (1) ◽  
pp. 41-61
Author(s):  
A. R. Kemp ◽  
W. G. Straitiff
Keyword(s):  
Tensile Strength ◽  
Natural Rubber ◽  
Physical Properties ◽  
Structural Features ◽  
Polymer Chains ◽  
Polymerization Reaction ◽  
Gel Structure ◽  
Gutta Percha ◽  
Cross Linkage

Abstract The low tensile strength of Buna-S gum stocks is generally believed to be due to failure to obtain effective cross-linkage as the result of vulcanization with sulfur and accelerators. Combined with this is the complete absence of crystallization of Buna-S on stretching which, in the case of natural rubber, reinforces and strengthens the vulcanized gel structure. The absence of crystallization in Buna-S can be explained on the basis of nonsymmetry along the polymer chains. Strictly speaking, Buna-S is not a true polymer, for ozonolysis shows that the styrene units are not spaced evenly in the chain but are grouped together in some locations. Ozonolysis also has proved the presence of vinyl groups attached to the chain, resulting from the polymerization of butadiene in the 1,2 instead of the 1,4 position. These vinyl groups must be unevenly spaced along the chain, and mixed trans and cis isomers must be present. Figure 1 illustrates the chemical units present in Buna-S, rubber, and gutta-percha hydrocarbons. In a Buna-S copolymer containing 24.5 per cent of styrene, there are six butadiene to one styrene units. It appears that about one butadiene in five polymerizes in the 1,2 position in the chain. It should be emphasized that, in Buna-S, ozonolysis has shown that no regular order exists in the location of A, B, and C units in the polymer. An entire lack of symmetry in the positioning of these units in the chain would be expected in view of the nature of the polymerization reaction.

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