C-Chains, branched

Figure 2. Proposed reaction mechanism for (a) insertion, (b) chain termination and (c) chain branching in the case of the Brookhart Ni-bis-imine polymerization catalyst. Large bulky substituents have been removed for clarity...

Thermal-oxidative degradation at 80 to 100 °C results in backbone cleavage at 120 to 130 °C, chain branching increases [797]. 

The assumption of quasi-stationarity can sometimes be justified if there is no significant chain branching, for example in FIBr fomiation at 200-3 00°C ... 

Hexane refers to the straight-chain hydrocarbon, C H branched hydrocarbons of the same formula are isohexanes. Hexanes include the branched compounds, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, and the straight-chain compound, / -hexane. Commercial hexane is a narrow-boiling mixture of these compounds with methylcyclopentane, cyclohexane, and benzene (qv) minor amounts of and hydrocarbons also may be present. Hydrocarbons in commercial hexane are found chiefly in straight-mn gasoline which is produced from cmde oil and natural gas Hquids (see Gasoline AND OTHER MOTOR fuels Gas,natural). Smaller volumes occur in certain petroleum refinery streams. 

The ability of C to catenate (i.e. to form bonds to itself in compounds) is nowhere better illustrated than in the compounds it forms with H. Hydrocarbons occur in great variety in petroleum deposits and elsewhere, and form various homologous series in which the C atoms are linked into chains, branched chains and rings. The study of these compounds and their derivatives forms the subject of organic chemistry and is fully discussed in the many textbooks and treatises on that subject. The matter is further considered on p. 374 in relation to the much smaller ability of other Group 14 elements to form such catenated compounds. Methane, CH4, is the archetype of tetrahedral coordination in molecular compounds some of its properties are listed in Table 8.4 where they are compared with those of the... 

The proposal that PVAc also has non-hydrolyzable long chain branches stems from the finding that PVA also possesses long chain branches. No/akura et a/.171 "07 suggested, on the basis of kinetic measurements coupled with chemical analysis, that chain transfer to PVAc involves preferential abstraction of backbone (methine) hydrogens (ca 5 1 v,v the acetate methyl hydrogens at 60 °C). 

Tab. 2.4 Effect of salt bridge orientation and side-chain branching at C y) on 3i4-helicity in water as investigated by CD > [177]...

A (Figure 4.9). The diameter of such a neck, 2.3 A, is sufficiently large for a linear C-C chain to pass, but too small to also be an equilibrium adsorption position. The largest compound allowed inside the pores is a linear molecule limited in length to four carbon atoms due to the distance between two subsequent necks [103]. Another example of shape-selective behavior is found in a Zn-based MOF able to encapsulate linear hexane while branched hexanes are blocked [104]. 

Figure 6.2. Typical ignition delay of an alkane fuel as a function of the initial mixture s temperature. Three different kinetic models are shown (a) High temperature chemistry only that is, no peroxy radical chemistry, (b) Same as (a), but the Q OOH chain-branching channel of the peroxy radicals has been considered, (c) Same as (b), bnt the concerted elimination of RO2 to alkene + HO2 has been considered. (Figure courtesy of Timothy Barckholtz, ExxonMobil Research and Engineering.)...

Figure 5.12 Examples of long chain branched molecules produced by macromer incorporation a) three-armed star b)"comb molecule,and c) complexly branched molecule...

Biesenberg, J. S. etal., J. Polym. Eng. Sci., 1976,16, 101-116 Polymerisation of methyl methacrylate initiated by oxygen or peroxides proceeds with a steady increase in velocity during a variable induction period, at the end of which a violent 90°C exotherm occurs. This was attributed to an increase in chain branching, and not to a decrease in heat transfer arising from the increasing viscosity [ 1 ]. The parameters were determined in a batch reactor for thermal runaway polymerisation of methyl methacrylate, initiated by azoisobutyronitrile, dibenzoyl peroxide or di-ferf-butyl peroxide [2],... 

Among the main molecular structural variables in EPDMs that are stipulated by catalyst systems and that affect the vulcanizate tensile properties we may mention molecular weight (MW) and MWD, degree of unsaturation (LG=C 1) and its distribution in the polymer, composition (C S) and monomer sequence length distribution along molecular chains, and long-chain branching if present. Effect of... 

Hinshelwood suggested the chain branching mechanism for reaction H2 + 02 C. Hinshelwood [50]... 

The outer chains, which are unbranched, are called A chains while the inner branched chains are called B chains. The single reducing group is contained in a unique chain called the C chain (Figure 8a). 

The chiral sites which are able to rationalize the isospecific polymerization of 1-alkenes are also able, in the framework of the mechanism of the chiral orientation of the growing polymer chain, to account for the stereoselective behavior observed for chiral alkenes in the presence of isospecific heterogeneous catalysts.104 In particular, the model proved able to explain the experimental results relative to the first insertion of a chiral alkene into an initial Ti-methyl bond,105 that is, the absence of discrimination between si and re monomer enantiofaces and the presence of diastereoselectivity [preference for S(R) enantiomer upon si (re) insertion]. Upon si (re) coordination of the two enantiomers of 3-methyl-l-pentene to the octahedral model site, it was calculated that low-energy minima only occur when the conformation relative to the single C-C bond adjacent to the double bond, referred to the hydrogen atom bonded to the tertiary carbon atom, is nearly anticlinal minus, A- (anticlinal plus, A+). Thus one can postulate the reactivity only of the A- conformations upon si coordination and of the A+ conformations upon re coordination (Figure 1.16). In other words, upon si coordination, only the synperiplanar methyl conformation would be accessible to the S enantiomer and only the (less populated) synperiplanar ethyl conformation to the R enantiomer this would favor the si attack of the S enantiomer with respect to the same attack of the R enantiomer, independent of the chirality of the catalytic site. This result is in agreement with a previous hypothesis of Zambelli and co-workers based only on the experimental reactivity ratios of the different faces of C-3-branched 1-alkenes.105... 

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