Solid-State C-13 NMR Studies of Vulcanized Elastomers XIII. TBBS Accelerated, Sulfur-Vulcanization of Carbon Black Filled Natural Rubber

1995 ◽  
Vol 68 (4) ◽  
pp. 551-562 ◽  
Author(s):  
Makio Mori ◽  
Jack L. Koenig
Keyword(s):  
Double Bond ◽  
Solid State ◽  
Carbon Black ◽  
Natural Rubber ◽  
Main Chain ◽  
Chain Scission ◽  
Nmr Studies ◽  
Double Bond Migration ◽  
Sulfur Vulcanization ◽  
Basic Network

Abstract Solid state C-13 NMR has been used to compare the chemistry of accelerated vulcanization of natural rubber using N-t-butyl-2-benzothiazole sulfenamide in the presence and absence of carbon black. The carbon black filler has an influence on the vulcanization chemistry in addition to its accepted role in reinforcment and stabilization. The basic network structure formation is modified to the extent that crosslink desulfurization from poly to monosulflde structures occurs earlier in the cure in the presence of carbon black. No main chain scission or double bond migration was detected.

Solid-State C-13 NMR Studies of Vulcanized Elastomers X. N-t-Butyl-2-Benzothiazole Sulfenamide Accelerated Sulfur Vulcanization of cis-Polyisoprene at 75.5 MHz

1992 ◽  
Vol 65 (2) ◽  
pp. 427-443 ◽  
Author(s):  
M. R. Krejsa ◽  
J. L. Koenig
Keyword(s):  
Solid State ◽  
Solid State Nmr ◽  
Chain Scission ◽  
Sulfur Concentration ◽  
Nmr Studies ◽  
Double Bond Migration ◽  
Sulfur Vulcanization ◽  
Equilibrium Swelling ◽  
Cis And Trans ◽  
Good Agreement

Abstract Accelerated sulfur vulcanized cis-polyisoprene was analyzed using C-13 solid-state NMR to determine the chemical microstructure of the network. Three formulations were analyzed consisting of varying accelerator/sulfur ratios. All formulations yielded similar network structures, but the amount of sulfurization varied with sulfur concentration. At low percent cure, only polysulfidic A-type cis-structures were found. For longer cure times, the A-type structures shortened to monosulfldic, and B-type polysulfidic structures, both cis and trans, were formed. The amount of trans-sulfurized product was constant with cure once this resonance appeared. No isomerization, chain scission, saturation, or double bond migration was detected. The NMR measurements appeared to show fairly good agreement with equilibrium swelling measurements.

Solid State Carbon-13 NMR Studies of Vulcanized Elastomers. III, Accelerated Sulfur Vulcanization of Natural Rubber

1987 ◽  
Vol 60 (2) ◽  
pp. 278-297 ◽  
Author(s):  
A. M. Zaper ◽  
J. L. Koenig
Keyword(s):  
Solid State ◽  
Natural Rubber ◽  
Nmr Spectra ◽  
Structural Modification ◽  
Main Chain ◽  
Nmr Studies ◽  
Structural Modifications ◽  
Sulfur Vulcanization ◽  
Chain Isomerization ◽  
Cyclic Sulfide

Abstract In summary, the solid state C-13 NMR technique has proven to be a significant method for the detection of crosslinks and other structural modifications in accelerated sulfur-vulcanized NR systems. When the amount of accelerator is high in proportion to the amount of sulfur used, the network structure appears to be simpler with less crosslinking, less main chain structural modification, and fewer cyclic sulfide structures as observed in the C-13 NMR spectra. Polysulfidic crosslinks have been detected in addition to polysulfides terminated by accelerator residues. Cis-to-trans chain isomerization is also evident in these vulcanizates.

Solid-State C-13 NMR Studies of Vulcanized Elastomers XVII. Effect of Carbon Black Grade on the Network Structure in Natural Rubber Vulcanizates

1997 ◽  
Vol 70 (4) ◽  
pp. 671-680 ◽  
Author(s):  
Makio Mori ◽  
Jack L. Koenig
Keyword(s):  
Solid State ◽  
Carbon Black ◽  
Natural Rubber ◽  
Network Formation ◽  
Physical Adsorption ◽  
Nmr Studies ◽  
Carbon Black Concentration ◽  
Effective Level ◽  
The Individual ◽  
Natural Rubber Vulcanizates

Abstract The vulcanization chemistry and network formation of carbon black filled natural rubber vulcanized with sulfur and TBBS were studied using solid-state C-13 NMR and equilibrium swelling measurements. A reduction in the sulfur rank of the A1 type sulfide and increased production of B1 type polysulfide are observed when the carbon black concentration increases in natural rubber. At the same loading level, the structural property or grade of carbon black does not affect qualitatively the type of sulfide formation. The efficiency of the intermolecular crosslinking over the whole range of sulfurizations is 45.7% for the unfilled vulcanizate. The extent of the chemical sulfurization reactions (NMR result) is constant with black incorporation, while the total network (swelling result) increases with increases in the black loading. The amount of physical entanglements, estimated from the comparison of the NMR and swelling results, is found to increase linearly with the carbon black concentration. The entanglements increase as a function of the 300% modulus, which suggests that the effective level of reinforcement depends on the nature of the individual carbon black. It is assumed that physical adsorption plays a major role in the polymer-filler interactions in the natural rubber/carbon black system.

Solid State Carbon-13 NMR Studies of Vulcanized Elastomers. II, Sulfur Vulcanization of Natural Rubber

1987 ◽  
Vol 60 (2) ◽  
pp. 252-277 ◽  
Author(s):  
A. M. Zaper ◽  
J. L. Koenig
Keyword(s):  
Solid State ◽  
Nmr Spectra ◽  
Molecular Motion ◽  
Main Chain ◽  
Repeat Unit ◽  
Crosslinking Agent ◽  
Nmr Studies ◽  
Structural Modifications ◽  
Chain Isomerization ◽  
Cyclic Sulfide

Abstract In summary, the solid-state C-13 NMR technique has proven to be a significant method for the detection of crosslinks and other structural modifications in sulfur-vulcanized NR systems. The use of sulfur as a crosslinking agent by itself generates a considerable amount of main-chain structural modifications. Cyclic sulfide structures and cis-to-trans chain isomerization are detected in addition to polysulfidic crosslinks which are found attached to different carbons of the NR repeat unit. The phenomenon of reversion has also been detected in this study. The nature of the spectral broadening in the NMR spectra of the highly cured vulcanizates has two origins. The broadening arises from lack of molecular motion in the system and from an increase in chemical shift dispersion due to the new structures formed with crosslinking.

Solid-State 13C NMR Characterization of Irradiation-Cross-Linked Natural Rubber

1987 ◽  
Vol 41 (3) ◽  
pp. 441-446 ◽  
Author(s):  
Dwight J. Patterson ◽  
Jack L. Koenig
Keyword(s):  
Solid State ◽  
Natural Rubber ◽  
Mobile Phase ◽  
Chain Scission ◽  
Structure Changes ◽  
Nmr Characterization ◽  
Cross Links ◽  
Gamma Irradiated ◽  
Trans Structure

Solid-state 13C NMR was used to characterize the structure changes produced in gamma irradiation in natural rubber. The structure of the irradiated natural rubber was found to be heterogeneous, consisting of a mobile phase and a semi-rigid phase. Cis-trans chain isomerization was detected in the mobile phase of the gamma-irradiated samples. The CP/MAS spectra of the more rigid phase contained resonances due to quaternary carbons arising from cross-links and vinyl end groups caused by main chain scission. The calculated values of β and G( X) agreed with earlier published results. Peroxide-cured natural rubber of an equivalent amount of network density showed a higher amount of trans structure than did the gamma-irradiated natural rubber.

Tensile Rupture of Rubber

1970 ◽  
Vol 43 (2) ◽  
pp. 222-228 ◽  
Author(s):  
A. G. Thomas ◽  
J. M. Whittle
Keyword(s):  
Tensile Strength ◽  
Critical Temperature ◽  
Low Temperature ◽  
Carbon Black ◽  
Natural Rubber ◽  
Growth Process ◽  
Abrupt Change ◽  
Main Chain ◽  
Low Temperature Crystallization ◽  
Temperature Crystallization

Abstract The dependence of tensile strength of a number of vulcanizates on temperature has heen studied. A critical temperature θc is found for natural rubber at which an abrupt change in strength occurs. This temperature depends on degree of crosslinking and also on the nature of the vulcanizing system. The presence of carbon black filler increases the strength above θc but has little influence on the value of θc or the strength at temperatures below it. The behavior can be explained qualitatively in terms of a change in mechanism of rupture from essentially a tear process above θc to a crack growth process below it. The influence of vulcanizing system is mainly due to changes in the nature of the crosslink rather than changes in regularity of the main chain as shown by the rate of low temperature crystallization.

Solid State Carbon-13 NMR Studies of Elastomers. XL N-t-Butyl Benzothiazole Sulfenimide Accelerated Sulfur Vulcanization of cis-Polyisoprene at 75 MHz

1993 ◽  
Vol 66 (1) ◽  
pp. 73-82 ◽  
Author(s):  
M. R. Krejsa ◽  
J. L. Koenig
Keyword(s):  
Solid State ◽  
Network Structure ◽  
Solid State Nmr ◽  
Cyclic Structure ◽  
Sulfur Concentration ◽  
Nmr Studies ◽  
Maturation Period ◽  
Sulfur Vulcanization

Abstract The network structure of TBSI-accelerated vulcanization of cis-polyisoprene was studied using C-13 solid-state NMR. The initial crosslink products consisted of A1c (cis) and A2c (cis) polysulfides. As the percent cure is increased, the A1c and A2c structures reduce in rank to monosulfides, and polysulfidic B1c (cis) and B1t (trans) structures are formed. During the maturation period C1c (cis) polysulfidic structures are also formed. The percent of sulfurization was shown to vary directly with sulfur concentration, while the efficiency of sulfurization (crosslink/cyclic-structure ratio) was shown to vary with accelerator content. TBSI-accelerated vulcanization was found to be more inefficient (lower crosslink/cyclic-structure ratio) than TBBS-accelerated vulcanization during the initial cure region. However, this results in shorter sulfur chains, which decreases the reactivity of TBSI vulcanizates as compared to TBBS vulcanizates during the reversion regime.

Studies on MBT-Accelerated Sulfur Vulcanization of Natural Rubber Reinforced with Carbon Black

1974 ◽  
Vol 47 (2) ◽  
pp. 251-265 ◽  
Author(s):  
S. Bhoumick ◽  
S. Banerjee
Keyword(s):  
Free Radical ◽  
Carbon Black ◽  
Stearic Acid ◽  
Natural Rubber ◽  
Radical Mechanism ◽  
Free Radical Mechanism ◽  
Sulfur Vulcanization ◽  
Polar Mechanism

Abstract Studies have been made on the mechanism of MBT accelerated sulfur vulcanization of natural rubber containing semi-reinforcing carbon black as a filler. DCP has been used as an aid to distinguish between free radical and polar mechanism. Results indicate that sulfuration by MBT and sulfur proceed by a free radical mechanism but it becomes polar when ZnO and stearic acid are also present. Carbon black does not interfere in the sulfuration but it gives rise to additional crosslinks.

CURE CHARACTERISTICS OF DEVULCANIZED RUBBER:THE ISSUE OF LOW SCORCH

2017 ◽  
Vol 90 (3) ◽  
pp. 536-549 ◽  
Author(s):  
Anu Mary Joseph ◽  
Benny George ◽  
K. N. Madhusoodanan ◽  
Rosamma Alex
Keyword(s):  
Solvent Extraction ◽  
Natural Rubber ◽  
Main Chain ◽  
Process Safety ◽  
Original Sample ◽  
Vulcanized Rubber ◽  
Sulfur Vulcanization ◽  
Natural Rubber Vulcanizates ◽  
Devulcanized Rubber

ABSTRACT We investigate the reasons behind the observed low scorch during the revulcanization of devulcanized rubber. Mechanically devulcanized carbon black filled natural rubber vulcanizates originally cured by conventional vulcanization (CV), semiefficient vulcanization (semi EV), efficient vulcanization (EV), and peroxide systems as well as buffing dust obtained from pre-cured tread with known formulation were used. Revulcanization of these devulcanized samples using sulfur/sulfonamide system led to the following observations; irrespective of the type of sulfur cure system used for the initial vulcanization of the rubber, (i) the devulcanized samples cured without pre-vulcanization induction time and (ii) devulcanized samples prepared from peroxide vulcanized rubber cured with scorch safety. Based on the earlier reports that solvent extraction of devulcanized rubber did not improve the scorch time during revulcanization, the role of zinc bound non-extractable moieties was investigated using devulcanized rubber prepared from activator-free vulcanizates, which disproved the role of such moieties. This confirmed that the scorch reducing moieties should be attached to the rubber main chain, which can be unreacted crosslink precursors and cyclic sulfides left after the initial accelerated sulfur vulcanization of the original sample. The ability of pre-vulcanization inhibitor to induce scorch safety when devulcanized rubber is revulcanized as such, without adding any virgin rubber, proved that mercaptobenzothiazole (MBT) generated from crosslink precursors is the cause of low scorch. Acetone extracted devulcanized rubber samples prepared from tetramethyl thiuramdisulfide (TMTD) cured natural rubber, which does not follow the MBT pathway when revulcanized, cured with scorch safety, which further proved the role of MBT. Based on the previous reports and our results, it is obvious that powdering of rubber vulcanizate and devulcanization processes have no role on the low process safety of these materials, but it is inherent to the initial accelerated sulfur vulcanization chemistry undergone by these materials.

Mechanisms Involved in the Recycling of NR and EPDM

1999 ◽  
Vol 72 (4) ◽  
pp. 731-740 ◽  
Author(s):  
M. A. L. Verbruggen ◽  
L. van der Does ◽  
J. W. M. Noordermeer ◽  
M. van Duin ◽  
H. J. Manuel
Keyword(s):  
Natural Rubber ◽  
Crosslink Density ◽  
Main Chain ◽  
Chain Scission ◽  
Ethylene Propylene ◽  
Temperature Range ◽  
Lower Reactivity ◽  
Ethylene Propylene Diene Rubber ◽  
Diene Rubber ◽  
Crosslink Densities

Abstract The thermochemical recycling of natural rubber (NR) and ethylene-propylene-diene rubber (EPDM) vulcanizates with disulfides was studied. NR sulfur vulcanizates were completely plasticized when heated with diphenyldisulfide at 200 °C. It could be concluded that both main chain scission and crosslink scission caused the network breakdown. NR peroxide vulcanizates were less reactive towards disulfide at 200 °C, and only reacted through main chain scission. For EPDM a temperature range of 200–275 °C was studied. In the presence of diphenyldisulfide at 200 °C there was almost no devulcanization of EPDM sulfur vulcanizates, and at 225 and 250 °C there was only slightly more devulcanization. A decrease in crosslink density of 90% was found when 2×10−4 mol diphenyldisulfide/cm3 vulcanizate was added and the EPDM sulfur vulcanizates were heated to 275 °C. EPDM peroxide vulcanizates showed a decrease in crosslink density of ca. 40% under the same conditions. The lower reactivity of EPDM towards disulfide compared with NR is the result of higher crosslink densities, the presence of a higher percentage of more stable monosulfidic crosslinks and the fact that EPDM is less apt to main chain scission relative to NR.

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