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Development of crosslinkable, thermoplastic polyurethanes for cardiovascular prostheses

Thesis (PhD (Process Engineering))--University of Stellenbosch, 2006.

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Main Author: Theron, Jacobus Petrus
Other Authors: Knoetze, J. H.
Format: Thesis
Language:English
Published: Stellenbosch : University of Stellenbosch 2008
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access_status_str Open Access
author Theron, Jacobus Petrus
author2 Knoetze, J. H.
author_browse Knoetze, J. H.
Theron, Jacobus Petrus
author_facet Knoetze, J. H.
Theron, Jacobus Petrus
author_sort Theron, Jacobus Petrus
collection Thesis
dc_rights_str_mv University of Stellenbosch
description Thesis (PhD (Process Engineering))--University of Stellenbosch, 2006.
format Thesis
id oai:scholar.sun.ac.za:10019.1/1315
institution Stellenbosch University (South Africa)
language English
last_indexed 2026-06-10T12:41:59.323Z
license_str Other — see source repository
provenance_str_mv Harvested via OAI-PMH from SUNScholar — Stellenbosch University Repository
publishDate 2008
publishDateRange 2008
publishDateSort 2008
publisher Stellenbosch : University of Stellenbosch
publisherStr Stellenbosch : University of Stellenbosch
record_format dspace
source_str SUNScholar — Stellenbosch University Repository
spelling oai:scholar.sun.ac.za:10019.1/1315 Development of crosslinkable, thermoplastic polyurethanes for cardiovascular prostheses Theron, Jacobus Petrus Knoetze, J. H. Bezuidenhout, D. Sanderson, R. D. University of Stellenbosch. Faculty of Engineering. Dept. of Process Engineering. Crosslinking Polyurethanes Thermoplastics Cardiovascular instruments, Implanted Polymeric composites Dissertations -- Process engineering Theses -- Process engineering Thesis (PhD (Process Engineering))--University of Stellenbosch, 2006. Existing thermoplastic polyurethanes (TPUs), used in the manufacturing of cardiovascular devices, still have unproven long-term biostability and may be prone to excessive plastic deformation when subjected to cyclic loading. These negative aspects can be attributed to, among other factors, the weak nature of virtual crosslinking through microphase separation. The modification and covalent crosslinking of existing medical grade polyurethanes with unsaturated acyl chlorides are thus proposed to improve these properties. A model compound study was used to find a suitable acyl chloride (4-pentenoyl chloride), confirm the intended carbamate nitrogen as successful reaction site and to optimize the chemistry of the reaction. Two medical grade polyurethanes, Pellethane® 2363- 80AE (Pellethane) and PurSil 35-80A (PurSil), were subsequently successfully modified with 4-pentenoyl chloride. The degree of modification could be accurately controlled (R2 = 0.99) to between 4.5% to 20.0% and between 11.5% to 18.5% for the respective polyurethanes. The degree of modification and method of crosslinking were then optimized to obtain the required mechanical properties (i.e. minimum hysteresis). The hysteresis and creep of the modified and crosslinked Pellethane were reduced by 42.5% and 44.0%, respectively, while the hysteresis of the modified and crosslinked PurSil was reduced by 12.9%. The chemical stability of Pellethane (control) modified Pellethane (15% modification) and crosslinked Pellethane (Pell15.0) was evaluated in an in vitro degradation study. The hysteresis of the crosslinked polymer was at least 27.5% better when compared to Pellethane, and showed a significant resistance to surface degradation (as studied with scanning electron microscopy). Although the soft phases in both polyurethanes are vulnerable toward degradation, it was not as pronounced in Pell15.0, mainly due to the restriction of chain movement resulting from the crosslinking. Small-diameter tubular constructs, with similar fiber and wall thicknesses, were electrospun from Pellethane and the 15% modified Pellethane. A standard electrospinning technique was used in the case of the former while in the case of the latter a novel “reactive” electrospinning technique was used for the in situ crosslinking of the novel material, while simultaneously forming the tubular constructs. It is suggested that the manufacturing of Pell15.0 be scaled up to produce adequate amounts of material to enable the extrusion and in vivo evaluation of e.g. pacemaker leads. A circulatory animal model, e.g. a senescent baboon model, could be used to evaluate and further optimize the electrospun tubular constructs. Doctoral 2008-08-04T08:23:24Z 2010-06-01T08:18:25Z 2008-08-04T08:23:24Z 2010-06-01T08:18:25Z 2006-12 Thesis http://hdl.handle.net/10019.1/1315 en University of Stellenbosch application/pdf Stellenbosch : University of Stellenbosch
spellingShingle Crosslinking
Polyurethanes
Thermoplastics
Cardiovascular instruments, Implanted
Polymeric composites
Dissertations -- Process engineering
Theses -- Process engineering
Theron, Jacobus Petrus
Development of crosslinkable, thermoplastic polyurethanes for cardiovascular prostheses
title Development of crosslinkable, thermoplastic polyurethanes for cardiovascular prostheses
title_full Development of crosslinkable, thermoplastic polyurethanes for cardiovascular prostheses
title_fullStr Development of crosslinkable, thermoplastic polyurethanes for cardiovascular prostheses
title_full_unstemmed Development of crosslinkable, thermoplastic polyurethanes for cardiovascular prostheses
title_short Development of crosslinkable, thermoplastic polyurethanes for cardiovascular prostheses
title_sort development of crosslinkable thermoplastic polyurethanes for cardiovascular prostheses
topic Crosslinking
Polyurethanes
Thermoplastics
Cardiovascular instruments, Implanted
Polymeric composites
Dissertations -- Process engineering
Theses -- Process engineering
url http://hdl.handle.net/10019.1/1315
work_keys_str_mv AT theronjacobuspetrus developmentofcrosslinkablethermoplasticpolyurethanesforcardiovascularprostheses