E, -caprolactone

Polyaza six-membered ring systems, 3, 1039-1086 Poly-e-caprolactone production, 7, 589 Polycyclic compounds nomenclature, 1, 14-28 Polyfuroxans, 6, 426 Polygermacyclopentanes, 1, 609... 

Ring opening of a lactone, e.g. of e-caprolactone with dihydroxy or trihydroxy initiators ... 

One variation in polyester intermediates that has roused some interest are those prepared by a ring-opening polymerisation of e-caprolactone and methyl-e-caprolactones with titanium catalysts and diol and triol initiators Figure 27.6). 

Poly (e -caprolactone) CAPA Solvay Environmental Petrochemistry... 

PHB poly(3-hydroxybutanoic acid) PHBV poly(3-hydroxybutanoic acid-co-3-hydroxyvaleric acid), ref. 105. CCAPA poly(e-caprolactone) FB100, ref. 456. 

Poly(f -caprolactone) (PCL), the most representative member of this polyester family, is obtained by the ring-opening polymerization of e-caprolactone. It is a low-7 (60°C), low-Tg (—60°C) semicrystalline polyester that presents mechanical properties resembling those of low-density polyethylene (Table 2.10). 

Lipases have also been used as initiators for the polymerization of lactones such as /3-bu tyro lac tone, <5-valerolactone, e-caprolactone, and macrolides.341,352-357 In this case, the key step is the reaction of lactone with die serine residue at the catalytically active site to form an acyl-enzyme hydroxy-terminated activated intermediate. This intermediate then reacts with the terminal hydroxyl group of a n-mer chain to produce an (n + i)-mer.325,355,358,359 Enzymatic lactone polymerization follows a conventional Michaelis-Menten enzymatic kinetics353 and presents a controlled character, without termination and chain transfer,355 although more or less controlled factors, such as water content of the enzyme, may affect polymerization rate and the nature of endgroups.360... 

A three-necked flask equipped with a condenser and stirrer was charged with the PET depolymerization product (0.05 mol of BHET and dimer in the ratio of 80 to 20 wt%), 0.05, 0.10, and 0.15 mol of e-caprolactone (in separate experiments), and 0.1 wt% of dibutyltin dilaurate. The reaction mixture was heated at 150°C for 2 h. The resulting co-oligomer (0.01 mol) was dissolved in 500 mL of tetrahydrofuran in a three-necked flask equipped with a condenser and a stirrer. After the temperature was raised to 67°C, a solution of 0.01 mL of hexamethylene diisocyanate in 50 mL of tetrahydrofuran was added dropwise. After heating and stirring the reaction mixture for 12 h, it was cooled and precipitated in ether. The polyurethane precipitate was collected by filtration and dried at 70°C for 12 h. 

Calderon classical catalyst system, 457 CAPA. See Poly(e-caprolactone) (CAPA, PCL)... 

OH-terminated poly(ethylene adipate-co-maleate), 97 OH-terminated poly(e-caprolactone), 98-99... 

See also PBT degradation structure and properties of, 44-46 synthesis of, 106, 191 Polycaprolactam (PCA), 530, 541 Poly(e-caprolactone) (CAPA, PCL), 28, 42, 86. See also PCL degradation OH-terminated, 98-99 Polycaprolactones, 213 Poly(carbo[dimethyl]silane)s, 450, 451 Polycarbonate glycols, 207 Polycarbonate-polysulfone block copolymer, 360 Polycarbonates, 213 chemical structure of, 5 Polycarbosilanes, 450-456 Poly(chlorocarbosilanes), 454 Polycondensations, 57, 100 Poly(l,4-cyclohexylenedimethylene terephthalate) (PCT), 25 Polydimethyl siloxanes, 4 Poly(dioxanone) (PDO), 27 Poly (4,4 -dipheny lpheny lpho sphine oxide) (PAPO), 347 Polydispersity, 57 Polydispersity index, 444 Poly(D-lactic acid) (PDLA), 41 Poly(DL-lactic acid) (PDLLA), 42 Polyester amides, 18 Polyester-based networks, 58-60 Polyester carbonates, 18 Polyester-ether block copolymers, 20 Polyester-ethers, 26... 

Preparation and characteristics of ABA type polycaprolactone-b-polydimethyl-siloxane block copolymers have been recently reported 289). In this study, ring-opening polymerization of e-caprolactone was achieved in melt, using a hydroxybutyl terminated PSX as the initiator and a catalytic amount of stannous octoate. Reactions were completed in two steps as shown in Reaction Scheme XIX. 

In recent years homoleptic lanthanide(III) tris(amidinates) and guanidinates have been demonstrated to exhibit extremely high activity for the ring-opening polymerization of polar monomers such as e-caprolactone and trimethylene... 

Broz, M.E., VanderHart, D.L. and Washburn, N.R. 2003. Structure and mechanical properties of poly(d,l-lactic acid)/poly(e-caprolactone) blends. Biomaterials 24 4181-4190. 

POLY(e-CAPROLACTONE) COPOLYMERS WITH GLYCOLIDE OR LACTIDE... 

Pego AP, Luyn MJAV, Brouwer LA, et al. In vivo behaviour of poly (1,3-trimethylene carbonate) and copolymers of 1,3-trimethylene carbonate with D,L-lactide or e-caprolactone Degradation and tissue response. J Biomed Mater Res, 2003, 67A, 1044—1054. 

Storey RF and Hickey TP. Degradable polyurethane networks based on D,L-lacdde, glycohde, e-caprolactone, and trimethylene carbonate homopolyester and copolyester triols. Polymer, 1994, 35, 830-838. 

Goma K and Gogolewski S. Biodegradable polyurethane implants U in vitro degradadon and calcification of materials from poly (e-caprolactone)-polyethylene) diols and various chain extenders. J Biomater Res, 2002, 60, 592-606. 

The general subject of lactone polymerization has been reviewed (7, 19). Polymerization of e-caprolactone can be effected by at least four different mechanisms categorized as anionic, cationic, coordination, and radical. Each method has unique attributes, providing... 

FIGURE 1 Continuous process for the manufacture of e-caprolactone by oxidation of cyclohexanone with peracetic acid. 

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). 

A related strategy has been employed to prepare a triblock copolymer of styrene and e-caprolactone by initiating the polymerization... 

FIGURE 2 Anionic, cationic, and coordination mechanisms of polymerization of e-caprolactone and related lactones. 

FIGURE 14 Different skeletal structures of PCL and its copolymers derived from the polymerization of e-caprolactone using mono- and polyfunctional initiators. 

Alkyl sulfonates are very effective cationic initiators of e-caprolactone, although only the more reactive methyl triflate and methyl fluorosulfate result in a high conversion. The mechanism of polymerization in the presence of these initiators is believed to involve methylation of the exocyclic carbonyl oxygen, followed by partial ring opening of the activated lactone by the counteranion (Fig. 

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