Acid catalyzed transesterification as a route to poly(3-hydroxybutyrate-co-epsilon-caprolactone) copolymers from their homopolymers.

Abstract:

:Copolymers of (R)-3-hydroxybutyric acid (HB) and epsilon-caprolactone (CL) with a composition ranging from 28 to 81 mol % of HB were synthesized by transesterification of the corresponding homopolymers in solution in the presence of 4-toluenesulfonic acid. The copolyesters were characterized with regard to their molecular weights, thermal properties, molar compositions, and average block length of repeating units by gel permeation chromatography (GPC), differential scanning calorimetry, (1)H NMR, and (13)C NMR, respectively. Random and microblock copolymers could be obtained depending on experimental conditions, with weight-average molecular weights of up to 20,000. The glass transition temperature decreased from 2 to -42 degrees C as the CL content was increased from 0 to 72 mol %. The melting temperature (T(m)) of the PCL phase decreased from 70 to 46 degrees C as the HB content changed from 0 to 47 mol %, while the T(m) of the PHB phase decreased from 177 degrees C to 163 degrees C as the CL content changed from 0 to 72 mol %. Matrix-assisted laser desorption ionization time-of-flight mass spectra of GPC fractionated samples allowed us to ascertain that copolymers rich in HB units have mostly hydroxyl and carboxyl end groups, while copolymers rich in CL units have mostly tosyl and carboxyl end groups.

journal_name

Biomacromolecules

journal_title

Biomacromolecules

authors

Impallomeni G,Giuffrida M,Barbuzzi T,Musumarra G,Ballistreri A

doi

10.1021/bm025525t

keywords:

subject

Has Abstract

pub_date

2002-07-01 00:00:00

pages

835-40

issue

4

eissn

1525-7797

issn

1526-4602

pii

bm025525t

journal_volume

3

pub_type

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