Diacid chlorides diol polymerization

Diacetoxybenzoic acid, synthesis and polymerization of, 116-118 Diacid, anhydride, and diol reaction, 97 Diacid chloride-diol solution reactions, 75-77... 

The synthesis of block copolycondensates by condensation reactions has also been described very often indeed the ineluctable presence of reactive end groups makes these molecules especially suitable for reactions with dibasic acids, diisocyanates, diacid chlorides, diamines, diols, etc. Using this method it was for example possible to synthesize polycondensates in which crystalline blocks alternate with amorphous blocks similarly it makes possible the synthesis of high molecular weight polymers from polycondensates of relatively low degree of polymerization. 

In other examples, compounds in which a metal atom is already coordinated in a molecule can be used as a comonomer in an addition polymerization. Two examples involve the ferrocenes discussed in Chapter 6. The vinyl ferrocene molecule is shown in 7.14, and a similar vinyl manganese complex in 7.15.30 An alternative approach involves condensation polymerization. For example, if the R group in the ferrocene unit shown in 7.16 contains a hydroxyl group, it can be copolymerized with a diacid chloride. If it is an acid chloride, it can be copolymerized with a diamine. (This type of polymer is called a heteroannular chain if only one of the rings in the repeat unit is in the backbone, the polymer is called homoannular.)7 Similarly, the titanium complex shown in 7.17 is copolymerized with diacids or diols.30 Numerous other examples involving ferrocenes are discussed in Chapter 6. 

The synthetic scheme used for the preparation of the LC polymers reported here involves the random copolymerization of both aromatic and aliphatic components as shown in Fig. 1. Both the diol and hydroquinone components can react with nearly equal probability with the diacid chloride component. We therefore have three factors which can contribute to inhomogeneity in this polymer system (i) the polydispersity of chain length expected in a condensation polymerization, (ii) the distribution of diol and hydroquinone components in the polymer chain, and (iii) the presence of methyl substituents and bromine substituents on the hydroquinone and terephthalate groups, respectively, means that many isomeric structures are also possible. 

Poly(ester imide)s have been synthesized by Mallakpour et al. [53] via a route involving reaction of pyromellitic anhydride with I-leucine, then conversion of the resulting diacid into its diacid chloride, which in turn reacted with several diols (for example phenolphthalein, bisphenol-A, and 4,4 -hydroquinone) under microwave irradiation conditions (Scheme 14.24). The polymerization reactions were conducted in 10 min in a domestic microwave oven in a porcelain dish in which... 

Synthesis, under microwave irradiation conditions, of polyamides containing azobenzene units and hydantoin derivatives in the main chains has recently been proposed by Faghihi et al. [55]. Polycondensation of 4,4 -azodibenzoyl chloride with eight 5,5-disubstituted hydantoin moieties has been achieved in the presence of a small amount of o-cresol (Scheme 14.26). The polycondensations were performed in 8 min, in a domestic microwave oven, in a porcelain dish in which 1.0 mmol diacid chloride was mixed with an equimolar amount of diol in the presence of small amounts of o-cresol. The polymerization proceeded rapidly, compared with the bulk reactions under conventional conditions (8 min compared with 1 h), producing a series of polyamides in high yield and inherent viscosity between 0.35 to 0.60 dL g h... 

Polyesters were historically the first synthetic condensation polymers studied by Carothers in his pioneering work in the early 1930s. Commercial polyesters [30] were manufactured by polycondensation reactions, the methods commonly used being melt polymerization of diacid and diol, ester interchange of diester and diol, and interfacial polymerization (Schotten-Baumann reaction) of diacid chloride and diol. In a polycondensation reaction a by-product is generated which has to be removed as the reaction progresses. 

In 1975, Kellyprepared and characterized a number of polyesters based on 2,5-disubstituted furans in various states of reduction. In this study, 2,5-disubstituted-furan, -dihydrofuran, and -tetrahydrofuran monomers were polymerized using solution, melt-transesterification, ring-opening, and interfacial techniques. These monomers included diacids, diols, diacid chlorides, diesters, dicarboxylic acid anhydrides, as well as monomers based on 5-hydroxymethyl-2-furoic and tetrahydrofuroic acids and esters, and bycyclic lactones containing the tetrahydrofuran ring. A thorough review of previous work done in the area of poljnner synthesis, based on 2,5-disubstituted furan derivatives is reported. It is reported that when... 

In order to exploit the inductive effect of the amide bond on the hydrolysis of the ester linkage in the polymer backbone the amide and ester linkage should be ideally separated by one methylene unit. It was apparent that a hydroxyacetamide structure would yield such an linkage. Hydroxyacetamide amidediols were obtained in high yields as the thermodynamically favorable product upon heating glycolic acid with alkane diamine neat with removal of w ater (Barrows, 1982, 1988, 1994). The polymer is then obtained either by trans esterification polymerization of the diol (bis-hydroxyacetamides) with the desired diester of the diacid or by the reaction of bis-hydroxyacetamides with diacid chlorides (Scheme 3) (Barrows 1982, 1988, 1994). Poly (ester-amides) can be prepared from a wide variety of different bis-hydrox acetamide amidediols and diacids. 

The dibasic acid can also be converted into diacid chloride and then condensed with diol. There are basically two methods the first one is interfacial polymerization either at low or high temperature. The aromatic diol is converted to phenolate ion in aqueous alkali solution phase. In organic medium aromatic diacid chloride is taken. Under high stirring the reaction takes place at the interface between phenolate and acid chloride [39]. Phase transfer catalyst can also be used for carrying out the reaction in organic solvent. The reaction rate is much faster than the first method. 

The synthesis of aliphatic polyesters with high molecular weight, in order to achieve satisfactory mechanical properties, is considered as being one of the most difficult problems to be solved. Till today this can be achieved only by either using techniques such as ringopening polymerization of cyclic monomers (lactones) or with the use of chlorides of acids, which are very expensive and inappropriate for industrial scale use [14,15]. The production of high molecular polyesters using diacids and diols can proceed only by the addition of chain extenders or branched comonomers as is the case of Bionolle [16]. 

A convenient method for preparation of polyesters and polyamides in the laboratory is the reaction of diacid chlorides with diols and diamines respectively (i.e. Schotten-Baumann reactions). These reactions proceed rapidly at low temperatures and often are performed as interfacial polymerizations in which the two reactants are dissolved separately in immiscible solvents which are then brought into contact. The best known example of this is the nylon rope trick where a continuous film of nylon is drawn from the interface as illustrated in Fig. 2.3 for the preparation of nylon 6.10... 

Facile and rapid polycondensation reactions of N,N -(pyromellitoyl)-bis-L-leucine diacid chloride, N,N -(pyromellitoyl)-bis-L-phenylalanine diacid chloride, 4,4 -earbonyl-bis(phthaloyl-L-alanine) diacid chloride or 4,4 -(hexafluoroisopropylidene)-N,N -bis(phthaloyl-Lleucine) diacid chloride with several aromatic diols such as phenol phthalein, bisphenol-A, 4,4 -hydroquinone, l,8-dihydro5g anthraquinone, 1,5-dihydroxy naphthalene, 4,4-dihydroxy biphenyl and 2,4-dihydroxyacetophenone were reported by using a domestic microwave oven in the presence of a small amount of a polar otganic solvent such as o-cresol (Mallakpour and Habibi, 2003). The polymerization reactions occurred rapidly and are completed within 10-20 min, producing a series of optically active poly(ester-imide)s with good yields and moderate inherent viscosities. 

A process of polymerization has been described that starts with an acid chloride, and a hydroxy acid in xylene as a solvent. After reaction, the hydrogen chloride is neutralized. In the next step, additional diacid and aromatic diol is added, together with acetic anhydride. Thus the acetylated products are created on the fly in the polymerization vessel. Finally, the actual transesterification polycondensation is performed. ... 

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