Trimethylene ring opening polymerization

The four-membered oxetane ring (trimethylene oxide [503-30-0]) has much higher ring strain, and irreversible ring-opening polymerization can occur rapidly to form polyoxetane [25722-06-9] ... 

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... 

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... 

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].

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. 

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... 

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. 

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... 

Dai, S., Xue, L., Li, Z., 2011. Enzymatic ring-opening polymerization of trimethylene carbonate with macrodiol s3mthesis of block poly(ester-co-carbonate) for biomaterial preparation. ACS Catalysis 1, 1421-1429. 

Dakshinamoorthy, D., Pemch, F., 2011. Titanium complexes based on aminodiol hgands for the ring-opening polymerization of e-caprolactone, rac-p-butyrolactone, and trimethylene carbonate. Journal of Polymer Science Part A Polymer Chemistry 49, 5176—5185. 

Darensbourg, D.J., Choi, W., Ganguly, P., Richers, C.P., 2006. Biometal derivatives as catalysts for the ring-opening polymerization of trimethylene carbonate. Optimization of the Ca(II) salen catalyst system. Macromolecules 39, 4374—4379. 

Dobrzynski, P., Pastusiak, M., Bero, M., 2005. Less toxic acetylacetonates as initiators of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate ring opening polymerization. Journal of Polymer Science Part A Polymer Chemistry 43, 1913—1922. 

Fliedel, C., Mameri, S., Dagome, S., Aviles, T., 2014. Controlled ring-opening polymerization of trimethylene carbonate and access to PTMC-PLA block copolymers mediated by well-defined N-heterocycbc carbene zinc aUcoxides. Applied Organometallic Chemistry 28, 504-511. 

Guerin, W., Helou, M., Carpentier, J.-F., Slawinski, M., Brusson, J.-M., Guillaume, S.M., 2013. Macromolecular engineering via ring-opening polymerization (1) L-lactide/trimethylene carbonate block copolymers as thermoplastic elastomers. Polymer Chemistry 4, 1095-1106. 

Helou, M., Miserque, O., Brusson, J.M., Carpentier, J.F., GuiUame, S.M., 2010h. Metal triflates as highly stable and active catalysts for the immortal ring-opening polymerization of trimethylene carbonate. ChemCatChem 2, 306—313. 

Schmid, M., Guillaume, S.M., Roesky, P.W., 2014. 3-Diketiminate rare earth borohydride complexes synthesis, structure, and catalytic activity in the ring-opening polymerization of 8-caprolactone and trimethylene carbonate. OrganometaUics 33, 5392—5401. 

Wu, H., Ji, Y., Li, Z., Wang, X., Zhang, Q., Ctii, S., Wu, W., Liu, J., Guo, K., 2015. Cationic ring-opening polymerization of trimethylene carbonate to a.w-dihydroxy telechehc and star-shaped polycarbonates catalyzed by reusable o-benzenedisulfonimide. Journal of Polymer Science Part A Polymer Chemistry 53, 729—736. 

Zhang, C., Liao, L., Gong, S., 2008. Zinc lactate-catalyzed ring-opening polymerization of trimethylene carbonate under microwave irradiation. Journal of Applied Polymer Science 110, 1236-1241. 

Conjugates of camptothecin were prepared. The polymeric matrixes were obtained by the ring-opening polymerization of s-caprolactone, glycolide, rac-lactide, or trimethylene carbonate. The synthesized polymers were coupled with various... 

BBL = -butyrolactone DTC = 2,2-dimethyl tri-methylene carbonate HTC = 2,2-(2-pentene-l,5-diyl)fri-methylene carbonate 1-MeTMC = 1-methyl trimethylene carbonate MMA = methylmethacrylate MMAO = modified methyMuminoxane PBD = polybutadiene PIP = polyiso-prene PHAs = polyhydroxyalkanoate PLA = polylactide ROP = ring-opening polymerization TMC = trimethylene carbonate. 

---