Chemical stability of polyether urethanes versus polycarbonate urethanes

Dipartimento di Bioingegneria, P.zza L. da Vinci, Milano, Italia.
Journal of Biomedical Materials Research 10/1997; 36(4):550-9. DOI: 10.1002/(SICI)1097-4636(19970915)36:43.0.CO;2-E
Source: PubMed

ABSTRACT The relative chemical stability of two commercially available polyurethanes-Pellethane, currently used in biomedical devices, and Corethane, considered as a potential biomaterial-was investigated following aging protocols in hydrolytic and oxidative conditions (HOC, water, hydrogen peroxide, and nitric acid) and in physiological media (PHM, phosphate buffer, lipid dispersion, and bile from human donors). The chemical modifications induced on these polymers were characterized using differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and Fourier transform infrared spectroscopy (FTIR). With the exception of nitric acid, all of the aging media promoted a mild hydrolytic reaction leading to a slight molecular weight loss in both polymers. When aged in water and hydrogen peroxide, Pellethane experienced structural modifications through microdomain phase separation along with an increase of the order within the soft-hard segment domains. The incubation of Pellethane in nitric acid also resulted in an important decrease of the melting temperature of its hard segments with chain scission mechanisms. Moreover, incubation in PHM led to an increase of the order within shorter hard-segment domains. FTIR data revealed the presence of aliphatic amide molecules used as additives on the Pellethane's surface. The incubation of Corethane under the same conditions promoted an almost uniform molecular reorganization through a phase separation between the hard and soft segments as well as an increase of the short-range order within the hard-segment domains. Incubation of this polymer in nitric acid also resulted in a chain scission process that was less pronounced than that measured for the Pellethane samples. Finally, lipid adsorption occurred on the Corethane sample incubated in bile for 120 days. Overall data indicate that polycarbonate urethane presents a greater chemical stability than does polyetherurethane.

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Available from: Maria Cristina Tanzi, Jul 28, 2015
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    • "Over the years there have been several attempts to replace the oxidatively susceptible polyether moiety with more oxidatively stable chemistries, creating low durometer biostable materials. For example, soft polycarbonate urethanes showed improved oxidative stability when the carbonate chemistry replaced the ether chemistry [8]. However, the carbonate moiety proved to be hydrolytically unstable [9]. "
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    ABSTRACT: Segmented polyurethane multiblock polymers containing polydimethylsiloxane and polyether soft segments form tough and easily processed thermoplastic elastomers (PDMS-urethanes). Two commercially available examples, PurSil 35 (denoted as P35) and Elast-Eon E2A (denoted as E2A), were evaluated for abrasion and fatigue resistance after immersion in 85 °C buffered water for up to 80 weeks. We previously reported that water exposure in these experiments resulted in a molar mass reduction, where the kinetics of the hydrolysis reaction is supported by a straight forward Arrhenius analysis over a range of accelerated temperatures (37-85 °C). We also showed that the ultimate tensile properties of P35 and E2A were significantly compromised when the molar mass was reduced. Here, we show that the reduction in molar mass also correlated with a reduction in both the abrasion and fatigue resistance. The instantaneous wear rate of both P35 and E2A, when exposed to the reciprocating motion of an ethylene tetrafluoroethylene (ETFE) jacketed cable, increased with the inverse of the number averaged molar mass (1/Mn). Both materials showed a change in the wear surface when the number-averaged molar mass was reduced to ≈16 kg/mole, where a smooth wear surface transitioned to a 'spalling-like' pattern, leaving the wear surface with ≈0.3 mm cracks that propagated beyond the contact surface. The fatigue crack growth rate for P35 and E2A also increased in proportion to 1/Mn, after the molar mass was reduced below a critical value of ≈30 kg/mole. Interestingly, this critical molar mass coincided with that at which the single cycle stress-strain response changed from strain hardening to strain softening. The changes in both abrasion and fatigue resistance, key predictors for long term reliability of cardiac leads, after exposure of this class of PDMS-urethanes to water suggests that these materials are susceptible to mechanical compromise in vivo.
    Biomaterials 07/2013; 34(33). DOI:10.1016/j.biomaterials.2013.06.049 · 8.31 Impact Factor
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    • "We also report on the properties of the degraded polymer after being exposed to acidic, alkaline and oxidative conditions. Although there are several reports on the in vitro [21] [22] and in vivo [23] [24] [25] degradation of polyurethanes, to our knowledge there is no reference on the degradative behaviour of both HMDI:BD:PCL and HMDI:D- TE:PCL segmented polyurethanes for biomedical purposes. "
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    ABSTRACT: Biodegradable segmented polyurethanes (BSPUs) were prepared with poly(caprolactone) as a soft segment, 4,4'-methylene bis (cyclohexyl isocyanate) and either butanediol (BSPU1) or dithioerythritol (BSPU2) as a chain extender. BSPU samples were characterized in terms of their physicochemical properties and their hemocompatibility. Polymers were then degraded in acidic (HCl 2N), alkaline (NaOH 5M) and oxidative (H(2)O(2) 30wt.%) media and characterized by their mass loss, Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Undegraded BSPU1 and BSPU2 exhibited different properties, such as the glass transition temperature T(g) of the soft segment (-25 vs. 4 degrees C), mechanical properties (600% vs. 900% strain to break) and blood coagulating properties (clotting time=11.46 vs. 8.13min). After acidic and alkaline degradation, the disappearance of the 1728cm(-1) band of polycaprolactone (PCL) on both types of BSPU was detected by FTIR. However, the oxidative environment did not affect the soft segment severely as the presence of PCL crystalline domains were observed both by DSC (melting temperature T(m)=52.8 degrees C) and XRD (2theta=21.3 degrees and 23.7 degrees ). By TGA three decomposition temperatures were recorded for both BSPU samples, but the higher decomposition temperature was enhanced after acidic and alkaline degradation. The formation of the porous structure on BSPU1 was observed by SEM, while a granular surface was observed on BSPU2 after alkaline degradation.
    Acta biomaterialia 12/2009; 6(6):2035-44. DOI:10.1016/j.actbio.2009.12.010 · 5.68 Impact Factor
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    • "PCNUs have attained popularity in the biomaterials market because of their similar mechanical properties to conventional polyurethanes with improved oxidative stability [2]. Tanzi et al. [14] compared the "
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    ABSTRACT: Polycarbonate-polyurethanes (PCNUs) have provided the medical device industry with practical alternatives to oxidation-sensitive polyether-urethanes (PEUs). To date, many studies have focused on PCNUs synthesized with 4,4'-methylene diphenyl-diisocyanate (MDI). The relative hydrolytic stability of this class of polyurethanes is actually quite surprising given the inherent hydrolytic potential of the aliphatic carbonate group. Yet, there has been little information reporting on the rationale for the material's demonstrated hydrolytic stability. Recent work has shown that PCNU materials have a strong sensitivity towards hydrolysis when changes are made to their hard segment content and/or chemistry. However, knowledge is specifically lacking in regards of the identification of cleavage sites and the specific nature of the biodegradation products. Using high-performance liquid chromatography, radiolabel tracers and mass spectrometry, the current study provides insight into the distribution of biodegradation products from the enzyme-catalyzed hydrolysis of five different PCNUs. The hydrolytic sensitivity of the materials is shown to be related to the distribution of products, which itself is a direct consequence of unique micro-structures formed within the different materials. While an MDI-based polymer was shown to be the most hydrolytically stable material, it was the only PCNU that produced its diamine analog, in this case 4,4'-methylene dianiline (MDA), as a degradation product. Given the concern over aromatic diamine toxicity, this finding is important and highlights the fact that relative biostability is a distinct issue from that of degradation product toxicity, and that both must be considered separately when assessing the impact of biodegradation on biomaterial in vivo compatibility.
    Biomaterials 09/2003; 24(17):2805-19. DOI:10.1016/S0142-9612(03)00081-4 · 8.31 Impact Factor
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