80109-30-4

Upstream product

• 57-57-8 β-Propiolactone 
• 503-66-2 3-hydroxypropionic acid 

Relevant academic research and scientific papers

A new synthetic route to poly[3-hydroxypropionic acid] (P[3-HP]): Ring-opening polymerization of 3-HP macrocyclic esters

A new method for the preparation of high molecular weight of Poly[3-hydroxypropionic acid] P[3-HP] by employing ring opening polymerization (ROP) of macrocyclic esters derived directly from 3-HP was discussed. Good control over the molecular weights of the P[3-HP] polymers was observed both from the pure trimer (n=3) as well as from a mixture of larger cyclics (n= 4 and 5). The ROP of the trimer without solvent at 80 °C was successfully performed. The results show that the partial formation of acrylate groups during the ROP in solution.

Macrocyclization under thermodynamic control. A theoretical study and its application to the equilibrium cyclooligomerization of β-propiolactone

A general treatment of macrocyclization reactions occurring under thermodynamic control is presented. The fundamental quantities on which the treatment is based are the effective molarities of the cyclic oligomers and the equilibrium constant for the intermolecular model reaction between monofunctional reactants (Kinter). Four typical cases have been considered, namely, addition and condensation of a monomer of the type A-B, addition of A-A, and addition of A-A + B-B. A critical comparison with the classical theory of Jacobson and Stockmayer is presented. It is shown that the phenomenon characterized by the critical monomer concentration (cut-off point) is a limiting phenomenon which would occur only for infinitely large values of Kinter. The treatment has been successfully applied to the DOS/DTC-induced cyclooligomerization of β-propiolactone in CDCl3 solution that yields well-behaved ring-chain equilibrates closely adhering to the theoretical model. Best fit of the experimental product distributions to the general equations gave the equilibrium constant (Kinter) of the intermolecular model reaction, as well as the effective molarities (EMi) for the cyclic oligomers from trimer to octamer. The EMi values decrease in proportion of the -2.5 power of the oligomerization degree, thus providing a strong indication that the oligomeric polylactones are essentially strainless. The extremely low value of Kinter (2.5) is responsible for the absence of a cut-off point, which is usually present in ring-chain polymeric equilibrates.

Macrocyclic Oligolactones by Oligomerization of Simple Lactones

The catalyst system K-t-butoxide/THF is useful not only for converting ε-caprolactone into the known cyclic oligomers (14-, 21-, 28-ring etc.) but also for preparing the unknown cyclic oligomers of δ-valerolactone (12-, 18-, 24-ring etc.) if large amounts of catalyst are used in the presence of t-butyl alcohol.With γ-butyrolactone, the acidity of the α-CH2 leads instead to a bicyclic aldol type condensation product for which there is evidence of subsequent dimerization to a tricyclic 10-ring dilactone. β-Propiolactone undergoes eliminative ring-opening to acrylic acid which is in equilibrium with acyclic homologues.In contrast, the catalyst system BF3/CH2Cl2 converts β-propiolactone (but not the other lactones) cleanly to cyclic oligomers (12-, 16-, 20-ring etc.).The driving force for these reactions is primarily the instability of the cis ester configuration in monolactones, the ester groups of the oligolactones adopting exclusively the trans ester configuration.Ring strain seems to contribute only in the case of β-propiolactone.