Condensation polymerization synthesis

Scheme 2.1 Condensation polymerization synthesis of a sulfonic acid cation exchange resin...

Miyakoshi, R., Yokoyama, A., and Yokozawa, T. (2008a) Development of catalyst-transfer condensation polymerization. Synthesis of 7t-conjugated polymers with controlled molecular weight and low polydispersity. Journal of Polymer Science Part A-Polymer Chemistry, 46,753-765. 

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. 

Representative condensation polymers are listed in Table I. The list is by no means exhaustive, but it serves to indicate the variety of condensation reactions which may be employed in the synthesis of polymers. Cellulose and proteins, although their syntheses have not been accomplished by condensation polymerization in the laboratory, nevertheless are included within the definition of condensation polymers on the ground that they can be degraded, hydrolytically, to monomers differing from the structural units by the addition of the elements of a molecule of water. This is denoted by the direction of the arrows in the table, indicating depolymerization. 

The synthesis of a given polymer molecule through condensation polymerization, on the other hand, is accomplished by a series of independent condensations, which ordinarily occur at intervals scattered... 

Two major approaches to the formation of materials of this type have involved the derivatization of preformed organic polymers with organometallic functions and the synthesis and polymerization of organometallic monomers that contain vinyl substituents For the transition metals, condensation polymerizations have also been investigated. However, the reactions have generally been conducted at elevated temperatures, and the resulting products have often not... 

Figure 1. The synthesis of sequential IPN above and simultaneous interpenetrating networks, SIN, below. For the synthesis of SIN, two different reactions operate simultaneously such as condensation polymerization and addition polymerization. Reproduced with permission from Ref. 23. Copyright 1981, Plenum Publishing.

Knani D, Gutman AL, Kohn DH (1993) Enzymatic polyesterification in organic media. Enzyme-catalyzed synthesis of linear polyesters. I. Condensation polymerization of linear hydroxyester. II. Ring-opening polymerization of e-caprolactone. J Polym Sci A Polym Chem 31 1221-1232... 

For the synthesis of block copolymers chain addition polymerization (ionic or radical) as well as condensation polymerization and stepwise addition polymerization can be used. 

Condensation polymerization and stepwise addition polymerization are, for example, applied for the preparation of block polyesters. The synthesis concepts are different from those of chain polymerization in that at least one monomer is an oligomer with one or two functional end groups, for example polytetrahy-drofurane with a molecular weight of several hundred and OH-end groups (see Example 3-23). If this oligomer partially replaces butandiol in the condensation polymerization with terephthalic acid (compare examples 4-1 and 4-2), a po-ly(ether ester) is obtained with hard ester segments and soft ether segments and with the properties of a thermoplastic elastomer. 

Synthesis, The first Fully alkyl/aryl-subsiiluted polymers were reported in 1980 via a condensation-polymerization route. In addition lo providing fully alkyl/aryl-Mihsiiuiled poly pliospha/enes. the versatility of ihe process has allowed the preparation of various functionalized polymers and copolymers. 

Synthesis. The first fully alkyl/aryl-substituted polymers were reported in 1980 via a condensation—polymerization route. The method involves, first, the synthesis of organophosphine-containing alkyl or aryl substituents, followed by the ready oxidation of the phosphine to a phosphorane with leaving groups suitable for a 1,2-ehmination reaction. This phosphorane is then thermally condensed to polymers in which all phosphoms atoms bear alkyl or aryl substituents. This condensation synthesis is depicted in Figure 2 (5—7,64). 

The direct synthesis of PPP by condensation polymerization represents one of the oldest preparations of a conjugated polymer. This is exemplified by the Ull-mann coupling of dihalobenzenes using copper powder [56] and by Wurtz [57, 58] chemistry where dihalobenzenes are reacted with sodium metal to give oligomeric PPPs [59]. 

Both electrochemical and chemical oxidative routes are most often utilized for the synthesis of PANI. In an interesting departure from the oxidative route, poly(phenylene amine imine) was prepared via a conventional condensation polymerization, as illustrated in Scheme 63 [302, 303]. Comparison of this structurally well-characterized polymer with oxidatively prepared PANI allowed confirmation of the PANI structure. However, the structure of PANI produced by electrochemical means is less understood. 

The chain-growth condensation polymerization leading to aromatic polyether can be applied to the synthesis of a well-defined poly(ether sul-fone) by the condensation polymerization of 25, which is different from other monomers for chain-growth condensation polymerization in that the nucleophilic site and electrophilic site are on each benzene ring connected with an electron-withdrawing group, a sulfonyl group (Scheme 94). In the polymerization of 25 in the presence of an initiator and 18-crown-6 in sulfolane at... 

It is important to clarify whether catalyst-transfer condensation polymerization is specific to polythiophene, or whether it is generally applicable to the synthesis of well-defined it-conjugated polymers. We investigated the synthesis of poly(p-phenylene), to see whether a monomer 28 containing no heteroatom in the aromatic ring would undergo catalyst-transfer polymerization. However, all polymers obtained in the polymerization with Ni(dppp)Cl2, Ni(dppe)Cl2, or Ni(dppf)Cl2 possessed low molecular weights and broad polydispersities. Nevertheless, we found that LiCl was necessary for opti-... 

Another route for the production of materials involves the reaction of hydrolysis-condensation of metal alkoxides with water. We study here the important case of amorphous silica synthesis. In this case [38,39,44], silicic acid is first produced by the hydrolysis of a silicon alkoxide, formally a silicic acid ether. The silicic acids consequently formed can either undergo self-condensation, or condensation with the alkoxide. The global reaction continues as a condensation polymerization to form high molecular weight polysilicates. These polysilicates then connect together to form a network, whose pores are filled with solvent molecules, that is, a gel is formed [45],... 

It is clear that Tgxp is a function of curing conversion or molecular weight (for linear polymers) at adiff. One can observe a noticeable difference between T xp and T for such processes of polymer synthesis as polyaddition or condensation polymerization reactions. It is especially important for polymers with high T . For many heat-resistant polymers, T is higher than the temperature limit of their chemical decomposition. We can never reach natural T for these polymers. For such polymers, one really measures only Tgxp, the value of which depends on the reaction conditions. For structure-glass transition temperature correlations of networks, T is the most important quantity. 

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