Condensation polymerization branching

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. 

The sulfonium precursor route may also be applied to alkoxy-substituted PPVs, but a dehydrohalogenation-condensation polymerization route, pioneered by Gilch, is favored 37]. The polymerization again proceeds via a quinomethide intermediate, but die syndicsis of the conjugated polymer requires only two steps and proceeds often in improved yields. The synthesis of the much-studied poly 2-methoxy-5-(2-ethylhexyloxy)-l,4-phenylene vinylene], MEH-PPV 15 is outlined in Scheme 1-5 33, 35]. The solubility of MEH-PPV is believed to be enhanced by the branched nature of its side-chain. 

Vinyl addition polymerizations, being chain reactions, are more complex than condensation polymerizations and they are generally more likely to include minor side reactions leading to branching or cross-linking. The structures of the pol3oneric products are consequently more difficult to establish with certainty. 

Keywords Acyclic diene metathesis polymerization, ADMET, Condensation polymerization Functionalized polymers, Negative neighboring group effect, Branched polyethylene... 

Condensation polymerizations (polycondensations) are stepwise reactions between bifunctional or polyfunctional components, with elimination of small molecules such as water, alcohol, or hydrogen and the formation of macromo-lecular substances. For the preparation of linear condensation polymers from bifunctional compounds (the same considerations apply to polyfunctional compounds which then lead to branched, hyperbranched, or crosslinked condensation polymers) there are basically two possibilities. One either starts from a monomer which has two unlike groups suitable for polycondensation (AB type), or one starts from two different monomers, each possessing a pair of identical reactive groups that can react with each other (AABB type). An example of the AB type is the polycondensation of hydroxycarboxylic acids ... 

The actual position of the linkages in a branched polymer, such as (2), will depend on the relative reactivities of the hydroxyl groups. These reactivities are known to be different both in monomeric and polymeric carbohydrates.28 In a study24 of the condensation polymerization of undo) W. II. Carothers, Trans. Faraday Soc., S3, 39 (1936) Chem. Rev., 8, 353 (1931) Ref. 12, pp. 31—132. 

In summary, the acid-catalyzed condensation polymerization of sugars in methyl sulfoxide results in the formation of copolymers of the sugars with formaldehyde. The glycosyl residues probably occur in blocks, instead of being evenly separated by methylene bridges. The polymers are highly branched, and the glycosyl residues appear to be substituted in a random fashion. 

Polysaccharides are naturally occurring polymers, which can be considered as derived from aldoses or ketoses by condensation polymerization. A polysaccharide derived from hexoses, for example, has the general formula (C6H]oOs)n. This formula, of course, tells us very little about the structure of the polysaccharide. We need to know what the monosaccharide units are and how many there are in each molecule how they are joined to each other and whether the huge molecules thus formed are straight-chained or branched, looped or coiled. 

Because of their uncomplicated syntheses, aromatic polyesters are the most widely studied class of highly branched polymers. The polyesters were prepared in a single step by condensation polymerization from aliphatic dihydroxy monoacids or by stepwise syntheses. 

Olefin metathesis (OM) has proven to be one of the most important advances in catalysis in recent years based on the application of this chemistry to the synthesis of polymers and biologically relevant molecules [1-10]. This unique transformation promotes chain and condensation polymerizations, namely ring opening metathesis polymerization and acyclic diene metathesis polymerization (ADMET). Applications of metathesis polymerization span many aspects of materials synthesis from cell-adhesion materials [11] to the synthesis of linear polyethylene with precisely spaced branches [12]. 

Figure 5.12 Formation of branched polymer by condensation polymerization of A2B monomer as proposed by Flory (1953).

Another advantage of the DPE functionalization methodology is that it can be used to prepare condensation macromonomers, 34, which are polymers with two polymerizable ftmctional groups at one chain end. This type of macromonomer can participate in step-growth (condensation) polymerization with other diftmctional monomers to form model comb-type, branched condensation copolymers. 

For a monodisperse polymer sample, d = 1. The ranges of d values change drastically with the different mechanisms of polymerization. The values of d are 1.01-1.05 in living polymerization (anionic, cationic, living free radical, etc.), around 1.5 in condensation polymerization or coupling termination of polymerization, around 2 in disproportionation reactions on polymerization, 2-5 for high-conversion olefins, 5-10 in self-acceleration on common free radical polymerization, 8-30 in coordination polymerization, and 20-50 in branching reactions on polymerization. 

Polymers are produced by one of two processes, addition or condensation polymerization. Addition polymerization occurs by one of three mechanisms, radical (e.g., low density branched polyethylene), cationic (e.g., butyl rubbers), or anionic (e.g., polystyrene). Condensation polymerization is used to produce Nylon 6,6 from adipic acid and hexamethylenediamine with the elimination of water. Industrially,... 

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