Polymerization aromatic condensation

The refractory compounds in the HMW DOM pool seems to be generated through abiotic reactions that act to link degradation products into macromolecules. These new chemical bonds create molecular structures that enhance the overall refractory nature of the DOM. The chemical changes lead to increased crosslinking, aromaticity, cyclization, esterification, and nitrogen depletion. The general types of chemical reactions responsible are oxidations, polymerizations, and condensations. Considerable debate exists as to whether these reactions are wholly abiotic or whether they are, at least in part, microbially mediated. 

The catalytic coke produced by the activity of the catalyst and simultaneous reactions of cracking, isomerization, hydrogen transfer, polymerization, and condensation of complex aromatic structures of high molecular weight. This type of coke is more abundant and constitutes around 35-65% of the total deposited coke on the catalyst surface. This coke determines the shape of temperature programmed oxidation (TPO) spectra. The higher the catalyst activity the higher will be the production of such coke [1],... 

Brooks and Taylor showed that heat treatment of coal tar and petroleum pitch forms a liquid crystal (mesophase) with dlscotlc symmetry. Generally, mesophase formation was assumed to occur by polymerization and condensation of smaller pitch molecules to form large planar aromatics. It is true that the molecular weight increases upon heat treatment, but our studies on carbon yield indicates that volatilization might be more important than polymerization and condensation. If so, the original isotropic pitch already may contain the mesogenlc species. 

The porous interior of the pellet provides a resistance to mass transfer, i.e., confines the volatiles, which increases reactive fragment concentrations. This promotes polymerization and condensation reactions which form the greater char fraction and condensed aromatics (Table III and Figure V) than reported for conventional pyrolysis. 

Mochida (58) developed a process in which a synthetic mesophase is produced from the HF/BF3 catalyzed polymerization of naphthalene or methyl naphthalene. HF/BF3 is a Bronsted acid that has been used to catalyze coal liquifaction and aromatic condensation. The aromatic resin (AR)-mesophase produced through this process is both more spinnable and more easily oxidized than that produced from... 

We have recently developed an effective synthetic methodology for the preparation of macrocyclic oligomers of aromatic condensation polymers and have investigated their ring opening polymerization chemistry. 

Polymerization and condensation are considered as side reactions during visbreaking process. They occur when part of the formed hydrocarbons recombines to produce relatively stable high molecular weight products, which include poly-aromatics with condensed aromatic structure that are coke precursors. 

Dehydrogenation of heavy oils followed by polymerization and condensation of free radicals from high molecular weight compounds (mainly aromatic hydrocarbon) lead to formation of coke. 

Fig. 13. Polymerization chemistry of phenol—formaldehyde condensation synthesis of novolac resia. The phenol monomer(s) are used ia stoichiometric excess to avoid geUation, although branching iavariably occurs due to the multiple reactive sites on the aromatic ring.

Synthesis and Properties. Polyquinolines are formed by the step-growth polymerization of o-aminophenyl (aryl) ketone monomers and ketone monomers with alpha hydrogens (mosdy acetophenone derivatives). Both AA—BB and AB-type polyquinolines are known as well as a number of copolymers. Polyquinolines have often been prepared by the Friedlander reaction (88), which involves either an acid- or a base-catalyzed condensation of an (9-amino aromatic aldehyde or ketone with a ketomethylene compound, producing quinoline. Surveys of monomers and their syntheses and properties have beenpubhshed (89—91). 

Condensation ofDianhydrides with Diamines. The preparation of polyetherknides by the reaction of a diamine with a dianhydride has advantages over nitro-displacement polymerization sodium nitrite is not a by-product and thus does not have to be removed from the polymer, and a dipolar aprotic solvent is not required, which makes solvent-free melt polymerization a possibiUty. Aromatic dianhydride monomers (8) can be prepared from A/-substituted rutrophthalimides by a three-step sequence that utilizes the nitro-displacement reaction in the first step, followed by hydrolysis and then ring closure. For the 4-nitro compounds, the procedure is as follows. 

The diacids are characterized by two carboxyHc acid groups attached to a linear or branched hydrocarbon chain. AUphatic, linear dicarboxyhc acids of the general formula HOOC(CH2) COOH, and branched dicarboxyhc acids are the subject of this article. The more common aUphatic diacids (oxaUc, malonic, succinic, and adipic) as weU as the common unsaturated diacids (maleic acid, fumaric acid), the dimer acids (qv), and the aromatic diacids (phthaUc acids) are not discussed here (see Adipic acid Maleic anhydride, maleic acid, and fumaric acid Malonic acid and derivatives Oxalic acid Phthalic acid and OTHERBENZENE-POLYCARBOXYLIC ACIDS SucciNic ACID AND SUCCINIC ANHYDRIDE). The bihinctionahty of the diacids makes them versatile materials, ideally suited for a variety of condensation polymerization reactions. Several diacids are commercially important chemicals that are produced in multimillion kg quantities and find appHcation in a myriad of uses. 

There have been a number of different synthetic approaches to substituted PTV derivatives proposed in the last decade. Almost all focus on the aromatic ring as the site for substitution. Some effort has been made to apply the traditional base-catalyzed dehydrohalogenation route to PTV and its substituted analogs. The methodology, however, is not as successful for PTV as it is for PPV and its derivatives because of the great tendency for the poly(u-chloro thiophene) precursor spontaneously to eliminate at room temperature. Swager and co-workers attempted this route to synthesize a PTV derivative substituted with a crown ether with potential applications as a sensory material (Scheme 1-26) [123]. The synthesis employs a Fager condensation [124] in its initial step to yield diol 78. Treatment with a ditosylate yields a crown ether-functionalized thiophene diester 79. This may be elaborated to dichloride 81, but pure material could not be isolated and the dichloride monomer had to be polymerized in situ. The polymer isolated... 

It is also possible to prepare them from amino acids by the self-condensation reaction (3.12). The PAs (AABB) can be prepared from diamines and diacids by hydrolytic polymerization [see (3.12)]. The polyamides can also be prepared from other starting materials, such as esters, acid chlorides, isocyanates, silylated amines, and nitrils. The reactive acid chlorides are employed in the synthesis of wholly aromatic polyamides, such as poly(p-phenyleneterephthalamide) in (3.4). The molecular weight distribution (Mw/Mn) of these polymers follows the classical theory of molecular weight distribution and is nearly always in the region of 2. In some cases, such as PA-6,6, chain branching can take place and then the Mw/Mn ratio is higher. 

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