Designing biostable polyurethane elastomers for biomedical implants

The chemical structure, synthesis, morphology, and properties of polyurethane elastomers are briefly discussed. The current understanding of the effect of chemical structure and the associated morphology on the stability of polyurethanes in the biological environments is reviewed. The degradation of conventional polyurethanes appears as surface or deep cracking, stiffening, and deterioration of mechanical properties, such as flex-fatigue resistance. Polyester and poly( tetramethylene oxide) based polyurethanes degrade by hydrolytic and oxidative degradation of ester and ether functional groups, respectively. The recent approaches to develop polyurethanes with improved long-term biostability are based on developing novel polyether, hydrocarbon, polycarbonate, and siloxane macrodiols to replace degradation-prone polyester and polyether macrodiols in polyurethane formulations. The new approaches are discussed with respect to synthesis, properties and biostability based on reported in vivo studies. Among the newly developed materials, siloxane-based polyurethanes have exhibited excellent biostability and are expected to find many applications in biomedical implants.

Long-term in vivo biostability of poly(dimethylsiloxane) / poly(hexamethylene oxide) mixed macrodiol-based polyurethane elastomers

The long-term biostability of a novel thermoplastic polyurethane elastomer (Elast-Eon(TM) 2 80A) synthesized using poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS) macrodiols has been studied using an in vivo ovine model. The material's biostability was compared with that of three commercially available control materials, Pellethane(R) 2363-80A, Pellethane(R) 2363-55D and Bionate(R) 55D, after subcutaneous implantation of strained compression moulded flat sheet dumbbells in sheep for periods ranging from 3 to 24 months. Scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy were used to assess changes in the surface chemical structure and morphology of the materials. Gel permeation chromatography, differential scanning calorimetry and tensile testing were used to examine changes in bulk characteristics of the materials. The results showed that the biostability of the soft flexible PDMS-based test polyurethane was significantly better than the control material of similar softness, Pellethane(R) 80A, and as good as or better than both of the harder commercially available negative control polyurethanes. Pellethane(R) 55D and Bionate(R) 55D. Changes observed in the surface of the Pellethane(R) materials were consistent with oxidation of the aliphatic polyether soft segment and hydrolysis of the urethane bonds joining hard to soft segment with degradation in Pellethane(R) 80A significantly more severe than that observed in Pellethane(R) 55D. Very minor changes were seen on the surfaces of the Elast-Eon(TM) 2 80A and Bionate(R) 55D materials. There was a general trend of molecular weight decreasing with time across all polymers and the molecular weights of all materials decreased at a similar relative rate. The polydispersity ratio, M-w/M-n, increased with time for all materials. Tensile tests indicated that UTS increased in Elast-Eon(TM) 2 80A and Bionate(R) 55D following implantation under strained conditions. However, ultimate strain decreased and elastic modulus increased in the explanted specimens of all three materials when compared with their unimplanted unstrained counterparts. The results indicate that a soft, flexible PDMS-based polyurethane synthesized using 20% PHMO and 80% PDMS macrodiols has excellent long-term biostability compared with commercially available polyurethanes. (C) 2004 Elsevier Ltd. All rights reserved.

Stress cracking and photodegradation behavior of polycarbonate. The combination of two major causes of polymer failure

This work investigates the effects of photodegradation on the environmental stress cracking resistance of polycarbonate (PC). Injection molded samples were exposed to the ultraviolet (UV) light for various times in the laboratory prior to solvent contact. The bars were then stressed with two different loads in a tensile testing machine under the presence of ethanol. During this period, the stress relaxation was monitored and, after unloading, the ultimate properties were evaluated. Complementary tests were done by size exclusion chromatography, UV-visible spectroscopy, scanning electron microscopy, and light microscopy. The results indicated that ethanol causes significant modification in PC, with extensive surface crazing as well as reduction in mechanical properties. The previous degraded samples showed a higher level of stress relaxation and a greater loss in tensile strength in comparison with the undegraded ones. The synergist action of photodegradation and stress cracking in PC may be a consequence of the chemical changes caused by oxidation.

An ESR and NMR study of the gamma radiolysis of a bisphenol-A based polycarbonate and a phthalic acid ester

A study of the gamma-radiolysis of the commercial polymers U-polymer, UP (Unitake) and polycarbonate, PC, (Aldrich) has been undertaken using ESR spectroscopy. The G-value of radical formation at 77 K has been found to be 0.31 +/- 0.01 for UP and 0.5 +/- 0.02 for PC. By using thermal annealing and spectral subtraction, the paramagnetic species formed on irradiation has been assigned. The effect of radiation on the chemical structure of UP and PC has been investigated at ambient temperature and at 423 K. The NMR results show that a new phenol type chain end is formed in the polymers on exposure to gamma-radiation. The G-value of formation of the new phenol ends was estimated to be 0.7 for PC (423 K) and 0.4 for UP (300 K). (C) 1998 John Wiley & Sons, Ltd.

New methods for the assessment of in vitro and in vivo stress cracking in biomedical polyurethanes

This article describes a new test method for the assessment of the severity of environmental stress cracking of biomedical polyurethanes in a manner that minimizes the degree of subjectivity involved. The effect of applied strain and acetone pre-treatment on degradation of Pellethane 2363 80A and Pellethane 2363 55D polyurethanes under in vitro and in vivo conditions is studied. The results are presented using a magnification-weighted image rating system that allows the semi-quantitative rating of degradation based on distribution and severity of surface damage. Devices for applying controlled strain to both flat sheet and tubing samples are described. The new rating system consistently discriminated between. the effects of acetone pre-treatments, strain and exposure times in both in vitro and in vivo experiments. As expected, P80A underwent considerable stress cracking compared with P55D. P80A produced similar stress crack ratings in both in vivo and in vitro experiments, however P55D performed worse under in vitro conditions compared with in vivo. This result indicated that care must be taken when interpreting in vitro results in the absence of in vivo data. (C) 2001 Elsevier Science Ltd. All rights reserved.

Study of the production of polyesters for polyurethanes at pilot plant scale

Dissertação para obtenção do grau de Mestre em Engenharia Química

Occurrence of Mansonella ozzardi diagnosed using a polycarbonate membrane in a riverside population of Lábrea in the Western Brazilian Amazon

Abstract: INTRODUCTION Mansonella ozzardi is a widely distributed filaria worm in the Amazon region. This study aimed to determine the prevalence of M. ozzardi infection in riverine communities of Lábrea municipality, Amazonas State, Brazil. METHODS A diagnostic blood filtration method in a polycarbonate membrane was used. RESULTS M. ozzardi was found in 50.3% of the sample, with the highest prevalence in farmers/fishermen (69.4%; χ 2 = -19.14, p<0.001). The prevalence was higher in longer-term residents (≥11 years; 60.2%). CONCLUSIONS M. ozzardi infection rates are high near the Purus River, much greater than those previously reported based on diagnosis using thick blood smears.

Novel Melt Transurethane Process for Cycloaliphatic Polyurethanes and Their Self-Organization for Nano-Materials

In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

Optical and Thermal Properties of Diethyl-(2R, 3R) (1)-tartrate Based Chiral Polyurethanes with Main Chain Amido Chromophores

The toluene diisocyanate based optically active chiral polyurethanes were synthesized according to the symmetry conditions. The noncentrosymmetric (both charge asymmetry and spatial asymmetry) environment were attained by the incorporation of the chiral units (diethyl-(2R,3R)(þ)-tartrate) and donor-acceptor building blocks in the main chain which induce a helical conformation in the macromolecular chain. A series of optically active polyurethanes containing chiral linkages in the polymer back bone have been synthesized by using DBTDL catalyst by incorporating the amido diols which were obtained by the aminolysis of e-caprolactone by using the diamines, diaminoethane, diaminobutane, and diaminohexane respectively. The effect of incorporation of the chiral molecule diethyl-(2R,3R)(þ)-tartrate on the properties of polyurethanes was studied by changing the chromophores and also by varying the chiral-chromophore composition. Various properties of polyurethanes were investigated by UV, Fluorescence, TG/DTA, XRD, polarimetric techniques, Kurtz-Perry powder techniques, etc.

Synthesis and Properties of Polyurethanes of Hexamethylene Di-Isocyanate with Multifunctional Chromophores in the Main Chain

Various polyurethanes containing photoactive bis(azo) and bis(o-nitrobenzyl) groups in the main chain were synthesized by polyaddition reactions of diols such as bis(4-hydroxyphenylazo)-2,20-dinitrodiphenylmethane, 4-hydroxy-3-methylphenylazo- 40-hydroxyphenylazo-2,20-dinitrodiphenylmethane and bis(4-hydroxy-3- methylphenylazo)-2,20-dinitrodiphenylmethane with hexamethylene di-isocyanate (HMDI), in dimethyl acetamide (DMAc) in the presence of di-n-butyltin dilaurate (DBTDL) as catalyst. All of them were characterized by IR, UV-vis, 1H NMR and 13C NMR spectra and also by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC).

Isosorbide based chiral polyurethanes: optical and thermal studies

A new class of chiral polyurethanes containing amido linkages in the polymer backbone have been synthesized by reacting toluene diisocyanate with isosorbide (IS) chiral moiety and the chromophores [N,N0-ethane- 1,2-diyl bis(6-hydroxy hexanamide), N,N0-butane-1,4-diyl bis(6-hydroxy hexanamide) and N,N0-hexane-1,6-diyl bis (6-hydroxy hexanamide)]. The corresponding chromophores were obtained by the aminolysis of e-caprolactone by using the diamines, diaminoethane, diaminobutane and diaminohexane, respectively. All the polymers were synthesized according to the symmetry conditions so as to obtain the non-centrosymmetric environment. A series of polyurethanes were synthesized by varying the chiral– chromophore composition. The polyurethanes developed were characterized by optical and thermal methods.