Ring trimethylene carbonate

Ling, J. Shen, Z. Zhu, W. Synthesis, characterization, and mechanism studies on novel rare-earth calixarene complexes initiating ring-trimethylene carbonate. J. Polym. Sci. A Polym. Chem. 2003, 41 (9), 1390-1399. 

Table 2 Ring-opening polymerization of lactones initiated by lanthanide complexes (CL = e-caprolactone LA = lactide TMC = trimethylene carbonate). 

Kinetic measurements of the ring-opening polymerization of trimethylene carbonate (TMC) versus the enchainment of oxetane and CO2 to provide poly (TMC) reveal that these processes in the presence of (salen)CrCl and an ammonium salt have similar free energies of activation (AG ) at 110°C. This similarity in reactivity coupled with the observation that in situ infrared studies of the copolymerization of oxetane and CO2 showed the presence of TMC during the early stages of the reaction has led to the overall mechanism for copolymer production shown in... 

Scheme 6.39 Ring-opening poiymerization of trimethylene carbonate and 5-vaieroiactone, respectiveiy, catalyzed by a thiourea derivative 40 in the presence of a base.

The ring-strain energy of oxetane is less than that of PO (106.7k] mol 1 versus llTZkJmoT1) hence, its copolymerization with C02 is less favored thermodynamically [3], Nevertheless, the copolymerization of oxetane and C02 occurs readily under similar catalytic conditions, producing poly(trimethylene carbonate),... 

A kinetic study of the ring-opening polymerization (ROP) of trimethylene carbonate similarly afforded AG at 383 K of 101.9 kj mol-1, a value which was very close in energy to that found for the production of poly(TMC) from oxetane and C02. Hence, based on these experimental findings, the formation of polycarbonate from the oxetane and C02 coupling reaction was shown to occur via two different or concurrent pathways-that is, the intermediacy of TMC formation, and the subsequent polymerization and/or direct enchainment of oxetane and C02 (Figure 8.16). The presence of small amounts of ether linkages in the copolymer also supported this conclusion. 

In another solvent-free process with the same lipase as above, trimethylene carbonate underwent an almost quantitative ring-opening polymerization in 120 h at 70 °C to form poly(trimethylene carbonate) [18]. No decarboxylation was detected (Scheme 4). w-Pentadecalactone was likewise polymerized with lipases in the absence of a solvent to form polyesters of high molecular weight [19]. 

Scheme 4. Lipase-catalyzed ring-opening polymerization of trimethylene carbonate to linear poly(trimethylene carbonate) [18].

The coordination polymerisation of cyclic carbonates with a six-membered ring in the molecule, such as trimethylene carbonate (l,3-dioxan-2-one) and 2,2-dimethyltrimethylene carbonate (5,5-dimethyl-l,3-dioxan-2-one) [148-150], carried out in the presence of metal carboxylates e.g. zinc stearate, tin-based catalysts such as the di(w-butyl)stannic diiodide-triphenylphosphine system [151] or porphinatoaluminium compounds such as (tpp)AlOR [149] is not accompanied with decarboxylation and yields the respective polycarbonates (Table 9.2). The ring cleavage during the polymerisation of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate in the presence of the above catalysts has been found [148,149,151] to occur at the C(0)-0 bond, resulting... 

Bisht, K.S. Svirkin, Y.Y. Henderson, L.A. Gross, R.A. Kaplan, D.L. Swift, G. Lipase-catalyzed ring-opening polymerization of trimethylene carbonate. Macromolecules 1997, 30 (25), 7735-7742. 

Huang, Q. Shen, Z. Zhang, Y. Shen, Y. Shen, L. Yuan, H. Ring-opening copolymerization of trimethylene carbonate and D,L-lactide by rare earth chloride. Polym. J. 1998, 30 (3), 168-170. 

Matsumura, S. Tsukada, K. Toshima, K. Novel lipase-catalyzed ring-opening copolymerization of lactide and trimethylene carbonate forming poly(ester carbonate)s. Int. J. Biol. Macromol. 1999, 25 (1-3), 161-167. 

Liao L, Zhang C, Gong S (2007) Microwave-assisted ring-opening polymerization of trimethylene carbonate in the presence of ionic liquid. J Polym Sci Polym Chem 45 5857-5863... 

Deng, F., and Gross, R.A. (1999) Ring-opening bulk polymerization of epsilon-caprolactone and trimethylene carbonate catalyzed by lipase Novozym 435. Int.J. Biol. Macromol., 25, 153-159. 

Furthermore, the ring-opening co-polymerization of BTMC with 5,5-dimethyl-trimethylene carbonate (DTC) by immobilized porcine pancreatic lipase (0.1 wt%) catalyzed in bulk copolymerization at 150°C for 24h [117]. Under these conditions, the highest molecular weight of poly(BTMC-co-DTC) of M =26 400 was obtained, with 83% monomer conversion. 

Matsumura, S., Tsukada, K., and Toshima, K. (1997) Enzyme-catalyzed ring-opening polymerization of l,3-dioxan-2-one to poly(trimethylene carbonate). Macromolecules, 30 (10), 3122-3124. 

IPPL with different size were employed for ring-opening copolymerization of 5-benzyloxy-trimethylene carbonate (BTMC) with 5,5-dimethyl-trimethylene carbonate (DTC) in bulk (33). 

Yu F, Zhuo R (2004) Synthesis and characterization of OH-Terminated poly(trimethylene carbonate)s by alcohol-initiated ring-opening polymerization in melt bulk without using any catalyst. Polym J 36 28-33... 

Ling, J., Zhu, W., Shen, Z., 2004. ControUing ring-opening copolymerization of e-caprolactone with trimethylene carbonate hy scandium tris(2,6-di- tert -butyl-4-methylphenolate). Macromolecules 37 (3), 758—763. 

Synthesis of poly(trimethylene carbonate) by ring-opening poiymerisation... 

Scheme 4.4 Cationic ring-opening pol3fmerisation of trimethylene carbonate according to the...

Scheme 4,5 Initiation, propagation, and intramolecular transesteriiication reactions in anionic ring-opening polymerisation of trimethylene carbonate.

Table 4.2 Properties of poly(trimethylene carbonate) of different molar masses obtained via ring-opening polymerisation...

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