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.

Thermo-responsive microphase separated supramolecular polyurethanes

The ability to generate very stable assemblies via non-covalent interactions has enabled materials to be constructed that were not feasible via traditional covalent bond formation processes. A series of low molecular mass bisurethane and bisurea polymers have been developed that form stable self-assembled networks through hydrogen bonding interactions. Thermo-responsive polymers were generated by end-capping poly(ethylene-co-butylene) or polybutadiene chains with the bisurethane or bisurea motif. Microphase separation is observed via TEM and small-angle X-ray scattering (SAXS) for the modified pseudo polymers and significant differences in the temperature dependence of microphase separation are analysed via SAXS. The importance of the polarity of the end groups is manifested in distinct temperature-dependent microphase separation behaviour. Information on the local hydrogen bonding structure is provided by wide-angle X-ray scattering and variable temperature FTI

Alternative syntheses of linear polyurethanes using masked isocyanate monomers

A range of linear polyurethanes featuring aliphatic, aromatic and ether residues have been prepared by co-polymerisation of novel 'masked' isocyanate A(2)-type monomers and diols. The reactive isocyanate monomers were generated in situ via the triphenylphosphine mediated decomposition of the heterocyclic disulfide, 1,2,4-dithiazolidine-3,5-dione. Two different synthetic approaches were examined and assessed for the construction of the novel A(2)-type monomers, which involved either coupling two 1,2,4-dithiazolidine-3,5-diones together through a spacer group or construction of 1,2,4-dithiazolidine-3,5-diones directly from diamines. The resulting polyurethanes were purified via solvent extraction and analysed using GPC, NMR and IR spectroscopic analyses. Molecular weight data were obtained and compared from both GPC and H-1 NMR (via end-group analysis) spectroscopic analysis. The thermal properties of the polyurethanes were determined using DSC and their solubility in common aprotic organic solvents was also assessed and related to their structural composition. (c) 2006 Elsevier B.V. All rights reserved.

Preparation and characterization of cross-linked starch polyurethanes

This study describes the preparation and characterization of new starch cross-linked polyurethanes produced by the reaction of native cornstarch with a propylene oxide toluene diisocyanate oligomer. Infrared analysis confirmed the occurrence of the reaction and solubility and swelling tests showed that it had led to cross-linked structures. These products were totally amorphous and displayed elastomeric properties associated with two T(g)s at -60 and 35 degrees C. (C) 2009 Elsevier Ltd. All rights reserved.

Enhancement of thermal stability, strength and extensibility of lipid-based polyurethanes with cellulose-based nanofibers

Cellulose was extracted from lignocellulosic fibers and nanocrystalline cellulose (NC) prepared by alkali treatment of the fiber, steam explosion of the mercerized fiber, bleaching of the steam exploded fiber and finally acid treatment by 5% oxalic acid followed again by steam explosion. The average length and diameter of the NC were between 200-250 nm and 4-5 nm, respectively, in a monodisperse distribution. Different concentrations of the NC (0.1, 0.5, 1.0, 1.5, 2.0 and 2.5% by weight) were dispersed non-covalently into a completely bio-based thermoplastic polyurethane (TPU) derived entirely from oleic acid. The physical properties of the TPU nanocomposites were assessed by Fourier Transform Infra-Red spectroscopy (FTIR), Thermo-Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), X-Ray Diffraction (XRD), Dynamic Mechanical Analysis (DMA) and Mechanical Properties Analysis. The nanocomposites demonstrated enhanced stress and elongation at break and improved thermal stability compared to the neat TPU. The best results were obtained with 0.5% of NC in the TPU. The elongation at break of this sample was improved from 178% to 269% and its stress at break from 29.3 to 40.5 MPa. In this and all other samples the glass transition temperature, melting temperature and crystallization behavior were essentially unaffected. This finding suggests a potential method of increasing the strength and the elongation at break of typically brittle and weak lipid-based TPUs without alteration of the other physico-chemical properties of the polymer. (C) 2012 Elsevier Ltd. All rights reserved.

Comparison between polyurethanes containing castor oil (Soft Segment) and cancellous bone autograft in the treatment of segmental bone defect induced in rabbits

The aim of this study is to compare polyurethanes containing castor oil (soft segment) in granular form compared to cancellous bone autograft applied to a segmental bone defect. Norfolk adult female rabbits - approximately 13 months of age with a mean body weight of 4.5 kg - are used. In both radial diaphyses, 1 cm osteoperiosteal segmental defects are created. The defect in the left radius is filled with the castor-oil-based polyurethane, and the right one, filled with cancellous bone autograft, collected from the left proximal humerus. The rabbits are euthanazed at 15, 30, 60, and 120 days postsurgery (5 animals/ period), for histological analyses. By radiographic analyses, at these time points, the bone regeneration is more evident and accelerated in the bone defects treated with the cancellous bone autograft. At 120 days postsurgery, the segmental bone defects treated with the cancellous bone autograft are totally reconstituted and remodeled, while the bone defects treated with polyurethane polymer have bone formation of 79%. Histological study shows that the polyurethane acts as a space filler, minimizing the local production of fibrous tissue. No granule degradation, resorption or any inflammatory reaction is detected. Thus, it is possible to conclude that the castor-oil-plant-based polyurethane - in the granule presentation - is biocompatible and osteointegrated, but does not show the same bone regeneration capacity as the cancellous bone autograft. © 2007 SAGE Publications.

Synthesis and characterization of healable waterborne polyurethanes.

241 p.

Sensitive methods for studying the environmental performance of protective coatings

The safe working lifetime of a structure in a corrosive or other harsh environment is frequently not limited by the material itself but rather by the integrity of the coating material. Advanced surface coatings are usually crosslinked organic polymers such as epoxies and polyurethanes which must not shrink, crack or degrade when exposed to environmental extremes. While standard test methods for environmental durability of coatings have been devised, the tests are structured more towards determining the end of life rather than in anticipation of degradation. We have been developing prognostic tools to anticipate coating failure by using a fundamental understanding of their degradation behaviour which, depending on the polymer structure, is mediated through hydrolytic or oxidation processes. Fourier transform infrared spectroscopy (FTIR) is a widely-used laboratory technique for the analysis of polymer degradation and with the development of portable FTIR spectrometers, new opportunities have arisen to measure polymer degradation non-destructively in the field. For IR reflectance sampling, both diffuse (scattered) and specular (direct) reflections can occur. The complexity in these spectra has provided interesting opportunities to study surface chemical and physical changes during paint curing, service abrasion and weathering, but has often required the use of advanced statistical analysis methods such as chemometrics to discern these changes. Results from our studies using this and related techniques and the technical challenges that have arisen will be presented.

Azide and Alkyne Terminated Polybutadiene Binders: Synthesis, Cross-linking, and Propellant Studies

In composite solid propellants, the fuel and oxidizer are held together by a polymer binder. Among the different types of polymeric binders used in solid propellants, hydroxyl terminated polybutadiene (HTPB) is considered as the most versatile. HTPB is conventionally cured using isocyanates to form polyurethanes. However, the incompatibility of isocyanates with energetic oxidizers such as ammonium dinitramide and hydrazinium nitroformate, the short pot life of the propellant slurry, and undesirable side reactions with moisture are limiting factors which adversely affect the mechanical properties of HTPB based propellant. With an aim of resolving these problems, HTPB was chemically transformed to azidoethoxy carbonyl amine terminated polybutadiene and propargyloxy carbonyl amine terminated polybutadiene by adopting appropriate synthesis strategies and characterizing them by spectroscopic and chromatographic techniques. This is the first report on 1,3-dipolar addition reaction involving azide and alkyne end groups for cross-linking HTPB. The blend of these two polymers underwent curing under mild temperature (60 degrees C) conditions through 1,3-dipolar cycloaddition reaction resulting in triazoletriazoline networks. The curing parameters were studied using differential scanning calorimetry. The kinetic parameter, viz., activation energy, was computed to be 107.6 kJ/mol, the preexponential factor was 2.79 x 10(12) s-(1), and the rate constant at 60 degrees C was computed to be 3.64 x 10-(5) s-(1). The cure profile at a given temperature was predicted using the kinetic parameters. Rheological studies revealed that the gel time for curing through the 1,3-dipolar addition is 280 min compared to 120 min for curing through the urethane route. The mechanical properties of the resultant cured polybutadiene network were superior to those of polyurethanes. The cured triazolinetriazole polymer network exhibited biphasic morphology with two glass transitions (T-g) at -56 and 42 degrees C in contrast to the polyurethane which exhibited a single transition at -60 degrees C. This was corroborated by associated morphological changes observed by scanning probe microscopy. The propellant processed using this binder has the advantages of improved pot life as indicated by the end of the mix viscosity which is 165 Pas as compared with 352 Pas for the polyurethane system along with a slow build- up rate. The mechanical properties of the propellant are superior to polyurethane with an improvement of 14% in tensile strength, 22% enhancement in elongation at break, and 12% in modulus.