Polyesters synthesis methods

The preceding discussions of the kinetics and molecular weight distributions in the step-growth polymerization of AB monomers are clearly exemplified by the esterification reactions of such monomers as glycolic acid or co-hydroxydecanoic acid. Therefore one method for polyester synthesis is the following ... 

The carboxy-hydroxy reaction (direct esterification) is the most straightforward method of polyester synthesis. It was first reported in the 1930s by Carothers10 12 and is still a very widely used method for the synthesis of polyesters from diacids and diols (Scheme 2.12) or from hydroxy acids (Scheme 2.13). Direct... 

The reaction between acid anhydrides and diols is another convenient method of polyester synthesis. The reaction proceeds in two steps with the formation of an intermediate hydroxy acid (Scheme 2.15). 

The use of silylated monomers is an interesting alternative method of aromatic polyester synthesis since the silylated gaseous by-products cannot participate in the reverse reaction, shifting polyesterification toward polymer formation. Reactions between silyl esters and acetates (Scheme 2.23) and reactions between silyl ethers and acid chlorides (Scheme 2.24) have been applied to the synthesis of linear265-267 and hyperbranched wholly aromatic polyesters202,268 269 (see Section 2.4.5.2.2). 

The most important method used in the preparation of polyamides is direct amidation, usually through the intermediate formation of a salt of the diamine and dicarboxylic acid, but without it in the case of aminoacids or for pairs of monomers that do not readily form a salt. Esters can react with diamines to form polyamides with liberation of alcohol or phenol. Diamines can be reacted with diamides yielding polyamides and freeing ammonia. Polyamides have been prepared by acidolysis of acyl derivatives of diamines (compare Section 5.4 for acidolysis in polyester preparation). Bis-anhydrides react with diamines to form polyamides and, if reacted further, polyimides. The low-temperature reaction of acid chlorides with diamines has been used, interfacially or as a solution technique, to prepare certain polyamides (compare Section 5.7 for related reactions in polyester synthesis). 

In recent years, the enzymatic synthesis of biodegradable polyesters was focused on the polycondensation method (22,23). Among the very few successful example of enzymatic ring-opening polymerization for polyesters synthesis, Novozyme-435 (immobilized lipase B from Candida antartica) has been proved an effective catalyst for polycaprolactone (PCL) synthesis in toluene (24). Considering the low cost and high recyclablity of IPPL, we also... 

The industrial synthesis methods of polyesters trace back to Carothers. Poly(ethylene terephthalate) was discovered by Whinfield and Dickson in the 1940s.At the same time, Poly(ethylene naphthalate) was described in the literature." The industrial production started soon afterwards by ICI and DuPont. 

Stabilisers of this type have been claimed as extremely effective UV absorbers for poly(ethylene-co-l,4-cyclohexanedimethylene terephthalate) [98-100], allowing the use of this material in outdoor applications. Developments in novel synthesis methods have improved the inherent stability of this class of additive, paving the way towards their more effective use in aromatic polyesters [101-106]... 

Another recent study on polyester synthesis through thiol-ene reactions for preparation of monomers from fatty-acid derivatives was described by Pang and co-workers [16]. Authors adopted the same approach for preparing aliphatic diols and diester from 10-undecen-l-ol, methyl 10-undecenoate and thiols. In parallel, they prepared aromatic diesters from methyl vanillate and a series of thermoplastic polyesters were synthesised by polycondensation of the diols and diesters using conventional transesterification methods. These materials were obtained with Mn values of 12-27 kDa and T values of -13 to 13 °C. 

Polylactie aeids or Polylactide are terms used to indicate the same biodegradable aUphatie polyester (Moore and Saunders, 1997). The difference in terminology indieates simply the synthesis method chosen to produce the polymer from lactic acid. The interest in this material started in the 1930s with the work of Carothers but the moleeular weight and the mechanical properties were weak. 

Practical methods for synthesis and elucidation of the optimum physical forms were developed at Du Pont (13). The violets fill the void in the color gamut when the inorganics are inadequate. The quinacridones may be used in most resins except polymers such as nylon-6,6, polystyrene, and ABS. They are stable up to 275°C and show excellent weatherabiUty. One use is to shade phthalocyanines to match Indanthrone Blue. In carpeting, the quinacridones are recommended for polypropylene, acrylonitrile, polyester, and nylon-6 filaments. Predispersions in plastici2ers ate used in thermoset polyesters, urethanes, and epoxy resins (14). 

The anionic method of polymerization is most useful for the synthesis of low molecular weight hydroxy-terminated oligomers and polymers that are to be further processed. For example, the treatment of hydroxy-terminated oligomers with isocyanates has been used to obtain polyester-urethanes (9,20), while triblock copolymers (PCL-PEG-PCL) are prepared by initiating the polymerization of e-caprolactone with the disodium alcoholate from polyethylene glycol (26). 

Two-step synthesis of sugar-containing polyesters by lipase CA catalyst was reported (Scheme 13)." Lipase CA catalyzed the condensation of sucrose with an excess of divinyl adipate to produce sucrose 6,6 -O-divinyl adipate, which was reacted with a,oo-alkylene diols by the same catalyst, yielding polyesters containing a sucrose unit in the main chain. This method conveniently affords... 

Terminal-functionalized polymers such as macromonomers and telechelics are very important as prepolymer for construction of functional materials. Single-step functionalization of polymer terminal was achieved via lipase catalysis. Alcohols could initiate the ring-opening polymerizahon of lactones by lipase catalyst. The lipase CA-catalyzed polymerizahon of DDL in the presence of 2-hydroxyethyl methacrylate gave the methacryl-type polyester macromonomer, in which 2-hydroxyethyl methacrylate acted as initiator to introduce the methacryloyl group quanhtatively at the polymer terminal ( inihator method ).This methodology was expanded to the synthesis of oo-alkenyl- and alkynyl-type macromonomers by using 5-hexen-l-ol and 5-hexyn-l-ol as initiator, respechvely. 

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