Synthesis chain growth

N. O. Elbashir and C. B. Roberts, Enhanced Incorporation of a-Olefins in the Fischer-Tropsch synthesis Chain-Growth Process over an Alumina-Supported Cobalt Catalyst in Near-Critical and Supercritical Hexane Media, Ind. Eng. Chem. Res., 2005, 44, 505-521. 

DMAPP may serve as the initiator for subsequent terpenoid synthesis (chain growth or polymerization) catalyzed by appropriate enzymes. These elementary reactions will be discussed in detail in the synthesis section. For the chemical understanding of the compounds, we use -OPP to denote pyrophosphate groups. In the biological literature, the pyrophosphate group is typically written as -PPi. 

Synthetic polymers are classified by their method of synthesis as either chain-growth or step-growth. The categories ate somewhat imprecise but nevertheless provide a useful distinction. Chain-growth polymers are produced by chain-reaction polymerization in which an initiator adds to a carbon-carbon double bond of an unsaturated substrate (a vinyl monomer) to yield a reactive inter-... 

The basic process steps in the Ziegler process are the synthesis of the tri-ethylaluminum catalyst, chain growth from an ethylene precursor, oxidation, and finally hydrolysis. 

Conditions that are important to all chemical reactions such as stoichiometry and reactant purity become critical in polymer synthesis. In step growth polymerization, a 2% measuring and/or impurity error cuts the degree of polymerization or the molecular weight in half. In chain growth polymerization, the presence of a small amount of impurity that can react with the growing chain can kill the polymerization. 

Table I summarizes the conditions used for network synthesis. The amount of TMSEMA was determined by the amount of HEMA required for a desired composition. The AIBN concentrations were kept low to insure adequate chain growth during the copolymerization (that is network formation). The obtained networks were transparent, homogeneous, tough, flexible materials demonstrating the utility of the approach. Desilylation of the networks was carried out by the use of...

The insertion of unsaturated molecules into metal-carbon bonds is a critically important step in many transition-metal catalyzed organic transformations. The difference in insertion propensity of carbon-carbon and carbon-nitrogen multiple bonds can be attributed to the coordination characteristics of the respective molecules. The difficulty in achieving a to it isomerization may be the reason for the paucity of imine insertions. The synthesis of amides by the insertion of imines into palladium(II)-acyl bonds is the first direct observation of the insertion of imines into bonds between transition metals and carbon (see Scheme 7). The alternating copolymerization of imines with carbon monoxide (in which the insertion of the imine into palladium-acyl bonds would be the key step in the chain growth sequence), if successful, should constitute a new procedure for the synthesis of polypeptides (see Scheme 7).348... 

Scheme 5. Structural and chronological overview of the macromonomers used for synthesis of dendronized polymers chain growth (a) and step growth polymerizations (b)...

The description of the product distribution for an FT reaction can be simplified and described by the use of a single parameter (a value) determined from the Anderson-Schulz-Flory (ASF) plots. The a value (also called the chain growth probability factor) is then used to describe the total product spectrum in terms of carbon number weight fractions during the FT synthesis. In the case... 

The readsorption and incorporation of reaction products such as 1-alkenes, alcohols, and aldehydes followed by subsequent chain growth is a remarkable property of Fischer-Tropsch (FT) synthesis. Therefore, a large number of co-feeding experiments are discussed in detail in order to contribute to the elucidation of the reaction mechanism. Great interest was focused on co-feeding CH2N2, which on the catalyst surface dissociates to CH2 and dinitrogen. Furthermore, interest was focused on the selectivity of branched hydrocarbons and on the promoter effect of alkali on product distribution. All these effects are discussed in detail on the basis... 

In Fischer-Tropsch synthesis the readsorption and incorporation of 1-alkenes, alcohols, and aldehydes and their subsequent chain growth play an important role on product distribution. Therefore, it is very useful to study these reactions in the presence of co-fed 13C- or 14 C-labeled compounds in an effort to obtain data helpful to elucidate the reaction mechanism. It has been shown that co-feeding of CF12N2, which dissociates toward CF12 and N2 on the catalyst surface, has led to the sound interpretation that the bimodal carbon number distribution is caused by superposition of two incompatible mechanisms. The distribution characterized by the lower growth probability is assigned to the CH2 insertion mechanism. 

Block copolymer synthesis from living polymerization is typically carried out in batch or semi-batch processes. In the simplest case, one monomer is added, and polymerization is carried out to complete conversion, then the process is repeated with a second monomer. In batch copolymerizations, simultaneous polymerization of two or more monomers is often complicated by the different reactivities of the two monomers. This preferential monomer consumption can create a composition drift during chain growth and therefore a tapered copolymer composition. 

For maximum yield of liquid hydrocarbons and minimum yield of gases, FT synthesis is optimised to produce predominantly heavy products (heavy paraffins),7 i.e., producing hydrocarbon chains as long as possible at maximum hydrocarbon chain growth probability. 

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