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Lipase-catalyzed synthesis of aliphatic polyesters via copolymerization of lactone, dialkyl diester, and diol.
Biomacromolecules 2008; 9(11):3246-51B

Abstract

Candida antarctica lipase (CALB) has been successfully used as catalyst for copolymerization of dialkyl diester with diol and lactone to form aliphatic polyesters. The polymerization reactions were performed using a two stage process: first stage oligomerization under low vacuum followed by second stage polymerization under high vacuum. Use of the two-stage process is required to obtain products with high molecular weights at high yields for the following reasons: (i) the first stage reaction ensures that the monomer loss via evaporation is minimized to maintain 1:1 diester to diol stoichiometric ratio, and the monomers are converted to nonvolatile oligomers; (ii) use of high vacuum during the second stage accelerates equilibrium transesterification reactions to transform the oligomers to high molecular weight polymers. Thus, terpolymers of omega-pentadecalactone (PDL), diethyl succinate (DES), and 1,4-butanediol (BD) with a M w of whole product (nonfractionated) up to 77000 and M w/ M n between 1.7 and 4.0 were synthesized in high yields (e.g., 95% isolated yield). A desirable reaction temperature for the copolymerizations was found to be around 95 degrees C. At 1:1:1 PDL/DES/BD monomer molar ratio, the resultant terpolymers contained equal moles of PDL, succinate, and butylene repeat units in the polymer chains. (1)H and (13)C NMR analyses were used to determine the polyester microstructures. The synthesized PDL-DES-BD terpolymers possessed near random structures with all possible combinations of PDL, succinate, and butylene units via ester linkages in the polymer backbone. Furthermore, thermal stability and crystallinity of a pure PDL-DES-BD terpolymer with 1:1:1 PDL to succinate to butylene unit ratio and M w of 85400 were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The copolyester was found to be a semicrystalline material with a T g of -34 degrees C and a T m of 64 degrees C, which degrades in a single weight loss step centered at T max = 408 degrees C.

Authors+Show Affiliations

Biomedical Engineering Department, Yale University, 55 Prospect Street, New Haven, Connecticut 06511, USA. zhaozhong.jiang@yale.edu

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

18939863

Citation

Jiang, Zhaozhong. "Lipase-catalyzed Synthesis of Aliphatic Polyesters Via Copolymerization of Lactone, Dialkyl Diester, and Diol." Biomacromolecules, vol. 9, no. 11, 2008, pp. 3246-51.
Jiang Z. Lipase-catalyzed synthesis of aliphatic polyesters via copolymerization of lactone, dialkyl diester, and diol. Biomacromolecules. 2008;9(11):3246-51.
Jiang, Z. (2008). Lipase-catalyzed synthesis of aliphatic polyesters via copolymerization of lactone, dialkyl diester, and diol. Biomacromolecules, 9(11), pp. 3246-51. doi:10.1021/bm800814m.
Jiang Z. Lipase-catalyzed Synthesis of Aliphatic Polyesters Via Copolymerization of Lactone, Dialkyl Diester, and Diol. Biomacromolecules. 2008;9(11):3246-51. PubMed PMID: 18939863.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Lipase-catalyzed synthesis of aliphatic polyesters via copolymerization of lactone, dialkyl diester, and diol. A1 - Jiang,Zhaozhong, Y1 - 2008/10/22/ PY - 2008/10/23/pubmed PY - 2008/12/25/medline PY - 2008/10/23/entrez SP - 3246 EP - 51 JF - Biomacromolecules JO - Biomacromolecules VL - 9 IS - 11 N2 - Candida antarctica lipase (CALB) has been successfully used as catalyst for copolymerization of dialkyl diester with diol and lactone to form aliphatic polyesters. The polymerization reactions were performed using a two stage process: first stage oligomerization under low vacuum followed by second stage polymerization under high vacuum. Use of the two-stage process is required to obtain products with high molecular weights at high yields for the following reasons: (i) the first stage reaction ensures that the monomer loss via evaporation is minimized to maintain 1:1 diester to diol stoichiometric ratio, and the monomers are converted to nonvolatile oligomers; (ii) use of high vacuum during the second stage accelerates equilibrium transesterification reactions to transform the oligomers to high molecular weight polymers. Thus, terpolymers of omega-pentadecalactone (PDL), diethyl succinate (DES), and 1,4-butanediol (BD) with a M w of whole product (nonfractionated) up to 77000 and M w/ M n between 1.7 and 4.0 were synthesized in high yields (e.g., 95% isolated yield). A desirable reaction temperature for the copolymerizations was found to be around 95 degrees C. At 1:1:1 PDL/DES/BD monomer molar ratio, the resultant terpolymers contained equal moles of PDL, succinate, and butylene repeat units in the polymer chains. (1)H and (13)C NMR analyses were used to determine the polyester microstructures. The synthesized PDL-DES-BD terpolymers possessed near random structures with all possible combinations of PDL, succinate, and butylene units via ester linkages in the polymer backbone. Furthermore, thermal stability and crystallinity of a pure PDL-DES-BD terpolymer with 1:1:1 PDL to succinate to butylene unit ratio and M w of 85400 were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The copolyester was found to be a semicrystalline material with a T g of -34 degrees C and a T m of 64 degrees C, which degrades in a single weight loss step centered at T max = 408 degrees C. SN - 1526-4602 UR - https://www.unboundmedicine.com/medline/citation/18939863/Lipase_catalyzed_synthesis_of_aliphatic_polyesters_via_copolymerization_of_lactone_dialkyl_diester_and_diol_ L2 - https://dx.doi.org/10.1021/bm800814m DB - PRIME DP - Unbound Medicine ER -