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Multicomponent segmented polyurethanes

Grant number: 11/09479-1
Support type:Scholarships in Brazil - Doctorate
Effective date (Start): August 01, 2011
Effective date (End): February 28, 2015
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
Principal researcher:Maria Isabel Felisberti
Grantee:Rafael Bergamo Trinca
Home Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
Associated research grant:10/17804-7 - Polymeric composites, AP.TEM

Abstract

This study aimed at the synthesis and characterization of segmented polyurethanes (SPUs), based on low molecular weight (2 kDa) macrodiols - poly(ethylene glycol), poly(L-lactide) and poly(trimethylene carbonate) (PEG, PLLA and PTMC, respectively) - and different diisocyanates (2,4-diisocyanato-toluene and 1,6-diisocyanato-hexane, 2,4-TDI and HDI, respectively) and chain extenders (1,4-butanediol and 2,2-bis-hydroxymethyl-propanoic acid, DMPA and BDO respectively). The PLLA and PTMC macrodiols were synthesized by ring-opening polymerization (ROP). The SPUs were obtained by a two-step route: synthesis of prepolymers from diisocyanates and macrodiols, followed by a chain extension step. The effects of the weight ratio of macrodiols on the physico-chemical and morphological properties of SPUs based on 2,4-TDI and BDO were studied. The ¹H NMR and GPC analysis revealed differences in reactivity of macrodióis, which resulted in differences in composition of the SPUs in relation to the reaction medium and in the molar mass distribution. Analysis by DSC, DMTA, AFM and swelling assays revealed that the intrinsic properties of the precursors were combined and modulated in SPUs. The combination of the three macrodiols results in SPUs with unique properties not found in binary and single component SPUs. The effects of the nature of the chain extenders and diisocyanates on the properties of ternary SPUs were also studied. The SPUs based on symmetrical diisocyanates (HDI) presents lower glass transition temperatures than those based on 2,4-TDI. Moreover, they are semi crystalline while SPUs based on 2,4-TDI are essentially amorphous. The morphology of the SPUs, typically of a dispersed phase in a matrix, is affected by the macrodiols ratio and by the nature of diisocyanates and chain extenders. The water swelling capability of the SPUs is governed by the PEG content and varies with temperature (temperature responsive SPUs) as well as with pH (pH responsive SPUs) when BDO is replaced with DMPA. SPUs with low PEG content and rich in PLLA were processed by electrospinning technique, resulting in nanofibrous porous films with elastomeric properties.

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Scientific publications (5)
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
FONSECA, LUCAS POLO; TRINCA, RAFAEL BERGAMO; FELISBERTI, MARIA ISABEL. Thermo-responsive polyurethane hydrogels based on poly(ethylene glycol) and poly(caprolactone): Physico-chemical and mechanical properties. Journal of Applied Polymer Science, v. 133, n. 25 JUL 5 2016. Web of Science Citations: 9.
TRINCA, RAFAEL BERGAMO; ABRAHAM, GUSTAVO A.; FELISBERTI, MARIA ISABEL. Electrospun nanofibrous scaffolds of segmented polyurethanes based on PEG, PLLA and PTMC blocks: Physico-chemical properties and morphology. Materials Science & Engineering C-Materials for Biological Applications, v. 56, p. 511-517, NOV 1 2015. Web of Science Citations: 21.
TRINCA, RAFAEL BERGAMO; FELISBERTI, MARIA ISABEL. Segmented polyurethanes based on poly(L-lactide), poly(ethylene glycol) and poly(trimethylene carbonate): Physico-chemical properties and morphology. EUROPEAN POLYMER JOURNAL, v. 62, n. SI, p. 77-86, JAN 2015. Web of Science Citations: 15.
TRINCA, RAFAEL BERGAMO; FELISBERTI, MARIA ISABEL. Influence of the Synthesis Conditions on the Structural and Thermal Properties of Poly( L- lactide)- b- Poly( ethylene glycol)- b- Poly( L- lactide). Journal of Applied Polymer Science, v. 131, n. 13 JUL 5 2014. Web of Science Citations: 8.
Academic Publications
(References retrieved automatically from State of São Paulo Research Institutions)
TRINCA, Rafael Bergamo. Multicomponent segmented polyurethanes. 2015. Doctoral Thesis - Universidade Estadual de Campinas (UNICAMP). Instituto de Química Campinas, SP.

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