Copolyesters reactions

Uses. Approximately 70% of the U.S. production is used to make poly(tetramethylene ether glycol) [25190-06-1] (PTMEG), also known as poly-THE, which is used in the production of urethane elastomers, polyurethane fibers (ether-based spandex), and copolyester—ether elastomers. PTMEG is also the fastest growing use (see PoLYETPiERS, TETRAHYDROFURAn). The remaining production is used as a solvent for the manufacture of poly(vinyl chloride) cements and coating, precision magnetic tape, a reaction solvent in the production of pharmaceuticals, and other miscellaneous uses. 

Hie most representative member of this class of polyesters is the low-molar-mass (M 1000-3000) hydroxy-terminated aliphatic poly(2,2/-oxydiethylene adipate) obtained by esterification between adipic acid and diethylene glycol. This oligomer is used as a macromonomer in the synthesis of polyurethane elastomers and flexible foams by reaction with diisocyanates (see Chapter 5). Hydroxy-terminated poly(f -caprolactonc) and copolyesters of various diols or polyols and diacids, such as o-phthalic acid or hydroxy acids, broaden the range of properties and applications of polyester polyols. 

Various environmentally degradable copolyesters obtained from reactions between diols and diacids have recently been commercially introduced. 

TPEs associating both rigid and soft polyester blocks have also been described. They cannot be obtained by the melt polyesterification used for polyesterether TPEs, since interchange reactions would yield random—rather than block — copolyesters. The preferred method involves the reaction of OH-terminated aliphatic and aromatic-aliphatic polyesters with chain extenders such as diisocyanates and results in copoly(ester-ester-urethane)s. 

As already discussed (Section 2.2.1.3), interchange reactions are also implicated in the formation of random copolyesters exhibiting the most probable molar mass distribution when polyester blends are melt mixed. They are also involved in the randomization of block copolyesters taking place in the melt upon heating.2,m 211... 

The polymerization of terephthaldehyde in the presence of triethoxyalu-minum391 or Uialkylaluminum392 (Tischchenko-Claisen reaction) yields random copolyesters containing ca. 1 1 mol ratio of p-methylenebenzoate and / -xyleneterephthalate units (Scheme 2.43). The reaction does not take place with sterically hindered aldehydes.392... 

Many random copolyesters and polyester-polycarbonates have also been prepared by ester interchange reactions in the molten state. Thus, poly(ethylene terephthalate-co -isophthalates) can be obtained by simple melt blending of PET and poly(ethylene isophthalate) (PEI) homopolyesters at 270°C. The copolymer changes gradually from a block type at the beginning of reaction to a random-type... 

The principal solvolysis reactions for PET are methanolysis with dimethyl terephthalate and ethylene glycol as products, glycolysis with a mixture of polyols and BHET as products, and hydrolysis to form terephthalic acid and ethylene glycol. The preferred route is methanolysis because the DMT is easily purified by distillation for subsequent repolymerization. However, because PET bottles are copolyesters, the products of the methanolysis of postconsumer PET are often a mixture of glycols, alcohols, and phthalate derivatives. The separation and purification of the various products make methanolysis a cosdy process. In addition to the major product DMT, methanol, ethylene glycol, diethylene glycol, and 1,4-cyclohexane dimethanol have to be recovered to make the process economical.1... 

Diacid chloride methods, 182-183 Diacid chlorides, 333 Diacid-diol copolyesters, 43 Diacid-diol polyesterifications, 66 Diacid-diol reaction, 95-97 Diacid method, 180-181 Diacids... 

By varying all the parameters of the process the authors prepared a set of copolyesters containing units and blocks with a tertiary amino group, which, in turn, could be transformed into a hydrophilic hydrochloride salt thus imparting water-compatibility to the initially organosoluble macromolecules. The principle involved was the formation of a block-type structure of chains in order to facilitate their further protein-like folding in an aqueous medium. It was shown that the main factors responsible for the blockiness were the relative reactivities of the (B) and (C) components (NMDEA and bisphenol) and the order of their addition to the reaction. 

Galbis et al. described a variety of carbohydrate-based linear polyesters 61 of the poly(alkylene dicarboxylate) type that were obtained by polycondensation reactions of the alditols 2,3,4-tri-(9-methyl-L-arabinitol (9) and 2,3,4-tri-O-methyl-xylitol (10), and the aldaric acids 2,3,4-tri-(9-methyl-L-arabinaric acid (26) and 2,3,4-tri-(9-methyl-xylaric acid (27), butanediol, and adipic acid were also used as comonomers [28]. Copolyesters of the poly(aIkylene-c )-arylene dicarboxylate) type were obtained using bisphenols as comonomers (Scheme 1). Chemical polycondensation reactions were conducted in bulk or in solution. Enzymatic polycondensation reactions of adipic acid with the above-mentioned alditols were carried out successfully using Lipozyme and Novozyme 435. The hydrolytic degradations of some of these polyesters were also described. 

By the mid 1970s, Tennessee Eastman also announced development of a copolyester consisting of 60/40 PHBA/polyethylene terephthalate (PET) by direction reaction of acetoxybenozic acid with PET in the melt [2], This system had the advantage of lower costs, but its use temperature was limited to 90 °C which is just above its Tg. In the early 1980s, researchers at Celanese reported... 

The potential for rapid randomizing processes in the copolyesters at elevated temperatures has been demonstrated conclusively by heating a mixture of the two homopolymers of PHBA and PHNA at 450 °C at a pressure of around several hundred psi [40]. Within a few seconds a viscous melt was observed to extrude from the cracks in the mold. Analysis of this material showed a structure consistent with the random 50/50 copolymer of HBA/HNA (see Figs. 18 and 19). We estimate that at this very high temperature the rate of interchain transesterification reactions corresponds to 1000 ester interchanges/chain/10 s. 

On the other hand, as opposed to the randomizing reactions which occur in the nematic melt if one anneals these copolyesters near their crystal nematic transition a completely different process appears to be operative. Thus several workers [11, 14], have reported that heating the HBA/HNA system near its melting point results in a dramatic increase in Tcn by approximately 50 °C. As... 

Figure 1. Reaction scheme for PCL/PLA block copolyester formation.

With regards to the crystallization behavior of these copolyesters(Figures 3 and 5), a single melting peak indicative of a PLLA crystalline phase is seen. The fact that the PCL phase does not exhibit the ability to crystallize following the polymerization of LLA may be attributed to the occurrence of ester exchange reactions that limit the average sequence... 

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