Accelerators classes

Nitrosamines. Findings that secondary amines, so common in mbber accelerators, can react with NO species to form the suspected human carcinogens, nitrosamines, have prompted active programs to develop alternative accelerators. Neither primary nor tertiary amines form stable nitrosamines and they are generally considered to be safe materials. The abiHty of each type of common mbber accelerator class to form nitrosamines has been summarized and depends on their 1°, 2°, or 3° nature (30). 

The comparisons between accelerator classes are shown in Figure 14.5. Figures 14.6 and 14.7 show comparisons of primary accelerators CBS, TBBS, MBS, and MBTS in NR and SBR, respectively. Major differences in scorch safety, cure rate, and modulus development are observed. 

FIGURE 14.5 Comparison of accelerator classes in natural rubber (NR). (From B.H. To, Rubber Technology, Hanser Verlag, Munich, Germany, 2001.)... 

For the purpose of polymer/additive analysis most applications refer to vulcanisate analysis. Weber [370] has determined various vulcanisation accelerators (Vulkazit Thiuram/Pextra N/Merkapto/AZ/DM) in rubbers using PC. Similarly, Zijp [371] has described application of PC for identification of various vulcanisation accelerator classes (guanidines, dithiocarbaminates, thiuramsulfides, mercapto-substituted heterocyclic compounds, thioureas, etc.). The same author has also... 

Participating in this study were the same 21 students described previously plus 1 student who was absent from school for the first task. The teacher of the accelerated class of sixth graders provided instruction for this group of students as well as for her own class. The students received 2 1/2 hours of instruction, spread over a two-week period. Students had the opportunity to study examples and to create their own problems. On the last day of instruction, students were asked to sort the same 20 problems they had sorted earlier. They were requested to sort the problems into the five categories of Change, Group, Compare, Restate, and Vary. They were permitted to put items they could not classify into a separate category called Other. ... 

The amount of difficulty encountered by the teachers in carrying out this task was somewhat surprising. Indeed, two of them had scores of 0 on the task. This contrasts with the sixth graders performance. The lowest score in the accelerated class was 8, and the lowest in the slower class was 3. One reason for the lack of cohesion in the teachers classifications may be the time constraint. They received information about all five situations at one time. It is possible that some of them simply did not understand but would do so if they had more instruction. Another reason may be that they have much more prior knowledge about story problems than did the students. Perhaps they experienced some conflict between certain parts of this prior knowledge and their newly acquired knowledge. 

Accelerator class Example Abbreviation Scorch safety Cure rate Expected sulfur cross-link length... 

ZnDBC is commonly referred to as an ultra-accelerator because the dithiocarba-mate class of rubber accelerators is known for imparting a very fast cure rate (just like the thiuram accelerator class). 

Diels-Alder reactions can be divided into normal electron demand and inverse electron demand additions. This distinction is based on the way the rate of the reaction responds to the introduction of electron withdrawing and electron donating substituents. Normal electron demand Diels-Alder reactions are promoted by electron donating substituents on the diene and electron withdrawii substituents on the dienophile. In contrast, inverse electron demand reactions are accelerated by electron withdrawing substituents on the diene and electron donating ones on the dienophile. There also exists an intermediate class, the neutral Diels-Alder reaction, that is accelerated by both electron withdrawing and donating substituents. 

Many methine cationic dyes, styrylic (141), pyrrolic. or amino-substituted (142) derivatives of thiazolium, possess interesting anthelmintic properties (143). This last class has been used as accelerators of the catabolism and activators of cellular exchanges (144). 

Although aimed at the introductory class, this simple experiment provides a nice demonstration of the use of GG for a qualitative analysis. Students obtain chromatograms for several possible accelerants using headspace sampling and then analyze the headspace over a sealed sample of charred wood to determine the accelerant used in burning the wood. Separations are carried out using a wide-bore capillary column with a stationary phase of methyl 50% phenyl silicone and a flame ionization detector. 

Dyeing accelerants Dyeing classes Dyeing of leather Dyeing paper Dyeing processes Dye initiators Dye-in-polymer systems Dye intermediates... 

Aliphatic-Garboxylics. There are only two herbicides present in this class, trichloroacetate [76-03-9] (TCA) and dalapon [75-99-0]. These are used primarily for the selective control of annual and perennial grass weeds in cropland and noncropland (2,299). Dalapon is also used as a selective aquatic herbicide (427). Dalapon and TCA are acidic in nature and are not strongly sorbed by sods. They are reported to be rapidly degraded in both sod and water by microbial processes (2,427). However, the breakdown of TCA occurs very slowly when incubated at 14—15°C in acidic sods (428). Timing not only accelerates this degradation but also increases the numbers of TCA-degrading bacteria. An HA has been issued for dalapon, but not TCA (269). 

Depending on the peroxide class, the rates of decomposition of organic peroxides can be enhanced by specific promoters or activators, which significantly decrease the energy necessary to break the oxygen—oxygen bond. Such accelerated decompositions occur well below the peroxides normal appHcation temperatures and usually result in generation of only one usehil radical, instead of two. An example is the decomposition of hydroperoxides with multivalent metals (M), commonly iron, cobalt, or vanadium ... 

Thiuram Sulfides. These compounds, (8) and (9), are an important class of accelerator. Thiurams are produced by the oxidation of sodium dithiocarbamates. The di- and polysulfides can donate one or more atoms of sulfur from their molecular stmcture for vulcanization. The use of these compounds at relatively high levels with litde or no elemental sulfur provides articles with improved heat resistance. The short-chain (methyl and ethyl) thiurams and dithiocarbamates ate priced 2/kg. Producers have introduced ultra-accelerators based on longer-chain and branched-chain amines that are less volatile and less toxic. This development is also motivated by a desire to rninirnize airborne nitrosamines. 

There are seven principal classes of accelerators and several miscellaneous products that do not fit into these classes. In addition, many proprietary blends of several accelerators are sold which are designed as cure packages for a specific appHcations. Choosing the best cure system is a responsibiUty of the mbber chemist and requites extensive knowledge of each accelerator type and its appHcabiUty in each elastomer. Table 5 shows a rule of thumb comparison of the scorch/cure rate attributes for the five most widely used classes of accelerators used in the high volume diene-based elastomers. 

It is common practice in the mbber industry for a compounder to use combinations of several accelerators in developing a cure system. Typically these cure systems are comprised of a primary accelerator and one or more secondary types. Primary accelerators are generally the thiazole and sulfenamide classes the secondary types (kickers) are the thiurams, dithiocarbamates, guanidines, and to a much lesser extent, certain amines and the dialkylphosphorodithioates (20). 

The thiophthalimide (CTP) and sulfenamide classes of retarders differ from the organic acid types by thek abiUty to retard scorch (onset of vulcanization) without significantly affecting cure rate or performance properties. Much has been pubUshed on the mechanism of CTP retardation. It functions particularly well with sulfenamide-accelerated diene polymers, typically those used in the the industry. During the initial stages of vulcanization, sulfenamides decompose to form mercaptobenzothiazole (MBT) and an amine. The MBT formed reacts with additional sulfenamide to complete the vulcanization process. If the MBT initially formed is removed as soon as it forms, vulcanization does not occur. It is the role of CTP to remove MBT as it forms. The retardation effect is linear with CTP concentration and allows for excellent control of scorch behavior. 

Many antioxidants ia these classes are volatile to some extent at elevated temperatures and almost all antioxidants are readily extracted from their vulcanizates by the proper solvent. These disadvantages have become more pronounced as performance requirements for mbber products have been iacreased. Higher operating temperatures and the need for improved oxidation resistance under conditions of repeated extraction have accelerated the search for new techniques for polymer stabilization. Carpet backiag, seals, gaskets, and hose are some examples where high temperatures and/or solvent extraction can combine to deplete a mbber product of its antioxidant and thus lead to its oxidative deterioration faster (38,40). 

The second class of grinding equipment is used to prepare dispersions. Typical of this class are baU and pebble mills, ultrasonic mills, and attrition mills. SoHds, eg, sulfur, antioxidants, accelerators, and zinc oxide, are generaUy ground on this equipment (see Size reduction). BaU mill action is assisted in some mills by a combination of dispersion circulation by an external pump and mechanical osciUation of an otherwise fixed nonrotary mill chamber. Where baU mill chambers are rotated it is necessary to experimentally estabHsh an optimum speed of rotation, the size and weight of the baU charge, and ensure the mills do not overheat during the grinding period. 

Accelerators are chemical compounds that iacrease the rate of cure and improve the physical properties of the compound. As a class, they are as important as the vulcanising agent itself. Without the accelerator, curing requires hours or even days to achieve acceptable levels. Aldehyde amines, thiocarbamates, thiuram sulfides, guanidines, and thiasoles are aU. classified as accelerators. By far, the most widely used are the thiasoles, represented by mercaptobensothiasole (MBT) and bensothiasyl disulfide (MBTS). 

Aceta2olamide, the best example of this class of diuretics (69,70), is rarely used as a diuretic since the introduction of the thia2ides. Its main use is for the treatment of glaucoma and some minor uses, eg, for the a1ka1ini2ation of the urine to accelerate the renal excretion of some weak acidic dmgs, and for the prevention of acute high altitude mountain sickness. 

Reactions involving ions can be favored to occur in the organic phase by use of phase-transfer catalysts. Thus the conversion of 1-chlorooctane to 1-cyanooctane with aqueous NaCN is vastly accelerated in the organic phase by 1.3 percent of tributyl (hexadecyl) phosphonium bromide in the aqueous phase. (Starks and Owens, J. Am. Chem. Soc., 95, 3613 [1973]). A large class of such promotions is known. 

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