Sebacic polycondensation with

Out of the polyamides (PA) mainly kapron (PA-6, the product of caprolactam polymerization) and different grades of nylon (PA-12, the product of dodecalactam polymerization PA-6.6 and PA-6, 10 synthesized by polycondensation of adipine or sebacate acid with hexamethylene diamine, and others) are of commercial value for processing into films, including anticorrosion... 

Dicarhoxylic Acid Diesters. Since imactivated esters, typically alkyl esters, show low reactivity toward lipase catalyst, the polycondensation with glycols was often performed under vacuum to produce polyesters of high molecular weight. Lipase MM-catalyzed polycondensation of diethyl sebacate and 1,4-butanediol under vacuum produced the polymer with Mw more than 2x 10 (98). 

PA-6,10 is synthesized from 1,6-hexamethylenediamine and sebacic acid, and PA-6,12 from 1,6-hexamethylenediamine and dodecanedioic acid. The melt synthesis from their salts is very similar to PA-6,6 (see Example 1). These diacids are less susceptible to thermal degradation.55 PA-6,10 can also be synthesized by interfacial methods at room temperature starting with the very reactive sebacyl dichloride.4 35 A demonstration experiment for interfacial polycondensation without stirring can be carried out on PA-6,10. In this nice classroom experiment, a polymer rope can be pulled from the polymerization interface.34... 

Alkyl esters often show low reactivity for lipase-catalyzed transesterifications with alcohols. Therefore, it is difficult to obtain high molecular weight polyesters by lipase-catalyzed polycondensation of dialkyl esters with glycols. The molecular weight greatly improved by polymerization under vacuum to remove the formed alcohols, leading to a shift of equilibrium toward the product polymer the polyester with molecular weight of 2 x 10" was obtained by the lipase MM-catalyzed polymerization of sebacic acid and 1,4-butanediol in diphenyl ether or veratrole under reduced pressure. ... 

The enzymatic synthesis of polyesters from activated diesters was achieved under mild reaction conditions. The polymerization of bis(2,2,2-trichloroethyl) glutarate and 1,4-butanediol proceeded in the presence of PPL at room temperature in diethyl ether to produce the polyesters with molecular weight of 8.2 x 10. Vacuum was applied to shift the equilibrium forward by removal of the activated alcohol formed, leading to the production of high molecular weight polyesters. The polycondensation of bis(2,2,2-trifluoroethyl) sebacate and aliphatic diols took place using lipases BC, CR, MM, and PPL as catalyst in diphenyl ether. Under the... 

Unactivated esters, typically alkyl esters, often show low reactivity toward lipase catalyst for transesterifications. In the case of the lipase-catalyzed polycondensation of dialkyl esters with glycols, the polymer of high molecular weight was not obtained. The molecular weight improved when vacuum conditions were used Mw reached more than 2 x 104 in the combination of diethyl sebacate and 1,4-butanediol catalyzed by lipase MM [30]. 

Poly(lactic acid) (PLA) has also been added to poly(SA) via melt polycondensation to produce the triblock copolymers poly(lactic acid-Wock-sebacic acid-Wock-lactic acid) (P(LA-block-SA-block-LA)) by Slivniak and Domb (2002). The PLA (d-, l-, and dl-) was incorporated by acetylation and addition to the PSA synthesis. They showed the formation of stable stereocomplexed particles with increased melting points and reduced solubility, and studied the degradation and drug release characteristics of the same (Slivniak and Domb, 2002). The stereocomplexes self-assemble as a consequence of the chirality in the PLA portions of the chains (Slivniak and Domb, 2002). 

The conditions used for a radical reaction could require a modification of the mechanochemical polycondensation. Such a polycondensation of poly ( -caprolactam) was carried out using sebacic acid dichloride as a condensing agent. For the mechanochemical polycondensation of all the other polymers, aliphatic and aromatic diamines were used. In all cases, the reaction was followed by determining chemically linked nitrogen, which decreased in the first case (owing to the fixation of acid dichloride) and increased in the remaining ones because of the reactions with diamines. 

The two homologous aliphatic diamines are commonly used as bifunctional monomers for polycondensation reactions. Hexamethylenediamine or 1,6-diaminohexane, Cf,H16N2 (CAS No. 124-09-4, PM Ref.No. 1840), which is most well-known as a polyamide (Nylon 66) monomer, is also copolymerized with sebacic acid to form Nylon 6/ 10, or with isophthalic acid. Besides that, it is applied as a curing agent for expoxy... 

Most of the reported work on the kinetics of catalysed polycondensation by transesterification is quite recent and in the main deals with the preparation of PET, though related work on other esters from ethylene glycol has been reported. Reinisch et al. [34] found that the melt polycondensation leading to poly(ethylene sebacate) in 3—4 mm films under vacuum, with manganous acetate as catalyst, was second order from p = 0.70 to p = 0.97. Rate coefficients are listed in Table 5 for this reaction, for the formation of poly(ethylene sebacate-co-terephthalate) and for PET. 

Uyama and coworkers [86] conducted the first ROP in ionic liquids using enzymatic catalysis. In this publication, the authors showed that ROP of e-caprolactone occurred successfully in BMIM PF6. However, after three days the molecular weights were less than 1000 Da and at least seven days were required to achieve molecular weights greater than 4 kDa. Uyama also investigated the polycondensation reaction between diethyl adipate or diethyl sebacate with 1,4-butanediol. However, molecular weights greater than 1.5 kDa were not achieved in either BMIM PF6 or BMIM BF4. 

Later, Braun et al. reported the synthesis of a broad range of polyesters from isosor-bide/isomannide and acid dichlorides via melt condensation [12], The acid chlorides used include linear C4-C16 alkanoyl, ortho/iso/terephthaloyl, and 1,8- and 2,6-naphthalenoyl. Relatively high aliphatic polyesters were obtained, with up to 60 000 (GPC) for poly(isosorbide sebacate). Contrary to the aliphatic polyesters, the semi aromatic polyesters are highly viscous at high temperatures, hampering polycondensation. The TgS recorded for polyesters obtained by melt polymerization of isosorbide or isomannide with terephthaloyl chloride were 147 and 156 °C, respectively. 

The formation of PA 1010 from sebacic acid and decamethylene diamine, like other AABB polyamides, is conducted using the nylon salt polycondensation technique. PA1012 is formed by the petro-based dodecanoic diacid (DDDA) and DMDA. PAIOT is formed by DMDA and terephthalic acid, a diacid with a benzene ring as a backbone. 

It has also been shown that lipase CA can produce reduced sugar-containing polyesters regioselectively from divinyl sebacate and sorbitol, in which sorbitol was exclusively acylated at the 1 and 6-positions (Scheme 23.11) [115]. Mannitol and meso-erythritol were also regioselectively polymerized with divinyl sebacate. The lipase CA-catalyzed polycondensation of adipic acid and sorbitol also took place in... 

Poly(ester carbonate)s with different compositions were synthesized by bulk polycondensation of DAS with diphenyl sebacate and diphenyl carbonate in the presence of zinc acetate as a catalyst [27]. Biodegradability was found to be highest for the poly(ester carbonate)s with carbonate contents of 10-20 mol per cent, and to decrease markedly for those with the carbonate content above 50 mol per cent. 

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