Synthesis and properties of novel segmented polyurethanes containing alkyl phosphatidylcholine side groups

In this article, we report the synthesis and properties of novel segmented polyurethanes containing alkyl phosphatidylcholine side groups. Alkyl phosphatidylcholine groups were attached to the hard blocks of the polyurethanes. A novel diol, 9-(2-hydroxy-1-hydroxymethyl-1-methyl-ethylcarbamoyl)-nonyl-phosphatidylcholine (HDEAPC), was synthesized and characterized by FTIR, ¹H-NMR and mass spectroscopy. Two types of polyurethanes, poly(ether urethane)s and poly(carbonate urethane)s, containing alkyl phosphatidylcholine side groups were synthesized using methylenebis(phenylene isocyanate) (MDI), polytetramethyleneoxide (PTMO), poly(1,6-hexyl-1,5-pentylcarbonate) diol (PHPCD), 1,4-butanediol (BDO) and HDEAPC. The obtained phosphatidylcholine polyurethanes had relatively high molecular weights and good mechanical strength, as characterized by GPC and Instron. XPS and contact angle studies revealed that there was enrichment of alkyl phosphatidylcholine side groups near the surface of the polyurethanes. Biocompatibility was evaluated by protein adsorption using conventional polyurethanes as references. The surface of phosphatidylcholine poly(carbonate urethane)s effectively suppressed protein adsorption.     

Amphiphilic segmented polyurethanes as surface modifying additives

Amphiphilic segmented polyetherurethanes were prepared from methylene diphenylene diisocyanate (MDI), poly(ethylene glycol) 1500 (PEG), and a fatty acid monoglyceride as a chain extender. The polymers were not soluble in water or methanol, but dissolved readily in organic solvents. The amphiphilic properties were demonstrated as a large hysteresis in the water contact angles, exceeding 110°. The amphiphilic polymers were shown to modify the surface properties of a poly(ether urethane) (PEU) and a poly(ether urethane urea) (PEUU) when added in 1–10 wt %, presumably due to migration of the additive to the surface. The surfaces of particularly the PEU blends became highly amphiphilic, exhibiting contact angles hystereses up to 90–100°. A surface saturation effect was observed at 5% added amphiphilic polymer. A difference in the behavior of PEU and PEUU was ascribed to differences in solubility of the additive in the matrix. On long-term exposure to water the PEUU blends increased their amphiphilic behavior.     

Synthesis of segmented polyurethanes based on furazan units

Linear polyurethane thermoplastics comprising furazan blocks soluble in organic solvents and having low melting points were obtained by nonequilibrium polycondensation of 3,4-bis(hydroxymethyl)furazan, butane-1,4-diol and 2,4-di-isocyanatotoluene. The thermal behavior of some copolymers was studied by DSC and TGA methods.     

Soy-oil-based segmented polyurethanes

Segmented polyurethanes were prepared from soy polyol, diphenyl methane diisocyanate (MDI), and ethylene glycol or butane diol as chain extenders. Samples were prepared with true hard-segment concentrations (HSC) of about 0, 10, and 40%. Both the soft MDI–polyol and hard MDI/diol segments are glassy at room temperature. These samples were also crosslinked through the polyfunctional polyol soft segment. Partial crystallinity and phase separation were detected in samples with 40% HSC, on the basis of DSC data. Small-angle X-ray scattering shows the existence of phase separation with domain sizes of about 10 nm in the 40% HSC samples, but not in the others. The distribution of domain sizes is considerably broader for the ethylene-glycol extended system compared with that for the butane-diol case. Although the presence of hard segments lowers the crosslink density, samples with higher HSC had higher glass transition temperatures, higher strengths, higher moduli, lower swelling, lower elongation at break, and lower impact strengths. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3178–3190, 2005     

Thermoelasticity of segmented polyurethanes

Various diphenylmethane diisocyanate-containing polyurethanes whose soft blocks differ in polarity and crystallizability have been investigated using deformation and scanning calorimetry to ascertain the contribution of different types of intermolecular interaction to elasticity of polyurethane elastomers. The phase composition of polyurethanes being investigated and its dependence on mechanical action have been analyzed on the basis of scanning calorimetry data. By measuring the mechanical work and thermal effect during extension (λ=1–3.5) deformation dependences of internal energy changes and the ratio of energy and entropy changes have been determined as well as energy contributions have been calculated. The data obtained for different temperatures demonstrate that a decrease in the fraction of energy changes is largely due to hard block structurization in the course of re-building the network of hydrogen bonds during deformation.     

Thermal stability of segmented polyurethanes

The thermal stabilities of two series of segmented polyurethane fibres have been compared with their chemical structure. The polyurethanes were synthesized from trimethylene diamine; 4, 4′ diphenylmethane di-isocyanate and two polyether based macrodi-isocyanates. Thermal stability was measured by thermogravimetric analysis and differential thermal analysis. By comparing the changes in weight loss and DTA peaks with chemical structure it has been found possible to separate soft segment from hard segment degradation.In the initial stages stability increases as soft segment concentration increases while the reverse is true in the later stages of degradation. The 100% soft segment polymer (polytetrahydrofuran) and the 100% hard segment polymer appear to behave anomalously. It is suggested that the hard segment has a stabilizing influence on the degradation of the soft segment. The results are discussed in the light of various theories of polyurethane degradation.     

Effect of thermal treatment on the micromechanical properties of segmented polyurethanes

The effects of thermal treatments on segmented polyurethanes were studied by low frequency mechanical spectrometry. Complementary informations on the morphology of microphases and characteristic temperatures were given by other techniques such as DSC and SAXS. We have shown that low temperature treatments affected the morphology of the soft phase. High temperature treatments induced modification of dynamic modulus spectra attributed to the evolution of the microphase separation rate and the degree of crystallinity of some hard domains.     

Synthesis and properties of liquid crystalline polyurethanes

1,4-Bis(p-hydroxybenzoate)phenylene was prepared using 1,4-bis(trimethylsiloxy)benzene and p-hydroxybenzoyl chloride as starting materials. A series of novel 1,4-bis(p-hydroxyalkoxybenzoate)phenylene were synthesized by reaction of 1,4-bis(p-hydroxybenzoate) phenylene with 3-brompropanol and 4-bromobutanol, respectively. The liquid crystal polyurethanes were prepared by 1,4-bis(p-hydroxyalkoxybenzoate)phenylene with MDI (p-methylene diphenylenediisocyanate) and 2,4-TDI(2,4-toluenediisocyanate), respectively. The thermotropic properties, the melting point (T _m) and the isotropization temperature (T _i) of the synthesized polyurethanes were characterized by DSC, IR and POM. It showed that all of the polyurethane polymers exhibited thermotropic liquid crystalline properties between 144°C and 260°C. The transition temperature (T _m and T _i) decreased with an increase in the length of the methylene spacer. __________ Translated from Journal of Qingdao University of Science and Technology, 2006, 27(1) (in Chinese)     

Thermal degradation of MDI-based segmented polyurethanes

Thermal degradations of 4,4′-diphenylmethane diisocyanate-based thermoplastic polyurethane elastomers were conducted and investigated as functions of heating conditions by using thermogravimetric analysis, ultraviolet-visible (UV-vis) spectroscopy, gel permeation chromatography (GPC), and Fourier transform infrared (FTIR) spectroscopy. The extent of degradation increased with increasing temperatures and times. The degradation was accompanied by crosslinking and was more significant under air than under nitrogen, indicating that a free-radical mechanism was involved. The degradation mainly was due to unstable hard segments and gave a red shift in the UV-vis spectra. The degradation, leading to considerable discoloration, was demonstrated by UV-vis spectroscopy, starting from 240 °C in air for 10 min. Heated in nitrogen for the same period of time, the samples did not show considerable discoloration until 280 °C. The UV-vis data suggested that the degradation occurred through cleavages of N H bonds and C H bonds on the hard segments. Chain scission of polymer main chains, as demonstrated by GPC data, occurred at a temperature as low as 200 °C in nitrogen, although cleavage of N H bonds was not detectable by UV-vis and FTIR spectroscopy at these conditions. FTIR spectroscopy also provided evidence of cleavage of N H bonds and depolymerization of urethane linkages. Irganox 1010 was found to be an efficient antioxidant. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4126–4134, 1999     

Synthesis and properties of polyester based polyurethanes

Hydroxyl terminated polyesters were prepared by a melt condensation technique using adipic acid and various diols. They were characterised by hydroxyl number, acid number and intrinsic viscosities in benzene. The polyesters were reacted with excess tolylene diisocyanate to yield isocyanate terminated prepolymers and subsequently cured with diols and diamines. These polymers were characterised by i.r. spectra, viscosity measurements and thermogravimetric analysis. The glass transition temperature of the polymers were found to be in the region ?25 to ?55. The influences of prepolymers and curing reagents are discussed with respect to the low temperature flexibility and thermal stability of the polyurethanes.     

Synthesis and properties of liquid crystalline polyurethanes

Liquid crystalline polyurethanes were prepared from 4,4′-bis(2-hydroxyethoxy)biphenyl (BHBP) and 2,4-tolylene diisocyanate (TDI). The effect of partial replacement of BHBP by 25–75 mol % poly(oxytetramethylene) diol (PTMO, M _n = 250) on the liquid crystalline properties was studied. The BHBP/TDI/PTMO polyurethanes were obtained by one- and two-step polyaddition. The polyurethanes were investigated by DSC, polarizing microscopy, x-ray, and IR spectroscopy. The molecular weight distribution was determined by GPC. The morphology of the polymers was investigated by the SALS method. Thermogravimetric investigations of the polyurethanes were also performed. All polyurethanes containing BHBP units have liquid crystalline properties. Partial replacement of BHBP by PTMO-250 considerably changes the phase transition temperatures and the range of mesophase occurrence. More homogeneous polyurethanes were obtained, if the two-step polyaddition method was applied. The polyaddition method affects the phase transition temperatures. © 1993 John Wiley & Sons, Inc.     

Studies on thermotropic main chain liquid crystalline segmented polyurethanes I. Synthesis and properties of polyurethanes from high aspect ratio mesogenic diol as chain extender

Thermotropic main chain liquid crystalline polyurethanes were prepared from 4-{[4-(6-hydroxyhexyloxy)phenylimino]methyl}benzoic acid 4-{[4-(6-hydroxyhexyloxy)phenylimino]methyl}phenyl ester (mesogenic diol) and 1,6-hexamethylene di-isocyanate. The effects of partial replacement of the mesogenic diol by 20-50 mol% of poly(tetramethylene oxide)glycol (PTMG) of varying molecular mass (M _n =650, 1000, 2000) on the liquid crystalline properties were studied. Structural characterization was carried out by FTIR spectroscopy and the molecular mass distribution was determined by GPC. Differential scanning calorimetry and hot stage polarizing optical microscopy were used to study the mesomorphic properties. It was observed that the partial replacement of the mesogenic diol by PTMG of varying molecular masses influenced the phase transitions and the occurrence of mesophase textures. When the molecular mass of PTMG was enhanced, a higher content of mesogenic agent was needed to obtain liquid crystalline properties.     

Shape-memory and biocompatibility properties of segmented polyurethanes based on poly(L-lactide)

A series of segmented poly(L-lactide)-polyurethanes (PLA-PUs) were synthesized by a two-step method, with oligo-poly(L-lactide) (PLA) as the soft segments and the reaction product of 2,4-toluene diisocyanate (TDI) and ethylene glycol (EG) as the hard segments. The shape-memory properties and biocompatibility of PLA-PUs were examined. The 50% compressed PLA-PUs could recover almost 100% to their original shape within 10°C from the lowest recovery temperature (22°C–37°C). In the recovery process the PLA-PU showed a maximum contracting stress in the range of 1.5–4 MPa. Cell incubation experiments show that PLA-PU has biocompatibility comparable to that of pure PLA. Therefore, this kind of polyurethane can be used for implanted medical devices with shape memory requirements. __________ Translated from Chemical Journal of Chinese Universities, 2007, 28(2): 371–375 [译自: 高等学校化学学报]     

Chemical structure and physical properties in polyester based segmented polyurethanes—II: Tensile properties

The tensile, stress relaxation and elastic recovery properties of the segmented polyurethanes described in Part I have been examined. As soft segment concentration (SSC) increased, the properties of the fibres varied from highly brittle through elastic to viscous. Elongation showed similar behaviour to that found in polyether based polyurethanes. Actual breaking stress went through a maximum at about 70% SSC. However stress at 50, 100 and 200% elongation showed rather more complicated behaviour. Stress relaxation went through a maximum at approximately 50–60% SSC, fell to a minimum at 82% then rose sharply. These results have been interpreted in terms of the morphology of the fibre. The modulus/volume fraction of hard segment (V_h) behaviour does not follow the pattern predicted by theory. An additional reinforcement seems to occur in the region of V_h = 0.3.     

Ultrasonic and dielectric studies of segmented ester polyurethanes

Ultrasonic and dielectric relaxation measurements are reported as a function of frequency and temperature for a series of segmented ester polyurethanes. Glass transitions for the ester block were determined using a combination of differential scanning calorimetry and dilatometry. The activation energy associated with the dipolar relaxation of the ester group was found to be sensitive to changes in the molecular weight and the relative proportions of the ester and isocyanate in the polymers. These data are discussed with reference to the morphological changes which are known to occur in these systems.     

Interaction of segmented polyurethanes and polyurethane-ureas with water

Sorption of water vapor by oligomeric homopolymers and triblock copolymers of ethylene oxide and propylene oxide, and by polyurethanes and polyurethane - ureas derived from them is discussed. While the sorption isotherms (plots of ψ₁ vs a₁, where ψ is he volume fraction of sorbed water and a₁ is activity) for most polymers investigated here are smooth and convex towards the abscissa, those found with polyurethane-ureas containing long hard blocks have a “toe” at low activities. The plots of a₁/ψ₁ vs a₁ are shown to facilitate the analysis of data and the interpretation in terms of the D'Arcy-Watt theory. Smooth isotherms are fitted by a simple equation with two parameters. The first is related to the limiting value, χ₀, (at ψ₁ → 0) of the χ parameter characterizing the polymer-water interaction. The dependences of χ₀ on the polymer composition (content of hard segments or oxyethylene units) can provide information on the interaction between hard and soft segments. The second parameter is used in the computation of parameters characterizing the clustering tendency of water molecules. This tendency depends mainly on the content of oxypropylene units but is also raised by urethane or urea groups, though not so much as by oxypropylene groups.     

The influence of soft segments on some properties of new transparent segmented polyurethanes

This work describes the synthesis and structure of the new segmented polyurethanes (SPURs) formed from an aliphatic diisocyanate [1,1′‐methanediylbis(4‐isocyanatocyclohexane] (Desmodur W^®) and unconventional sulfur‐containing chain extender [2,2′‐methylenebis([4,1‐phenylene]methylenesulfanediyl)diethanol]. Soft segments were poly(oxytetramethylene)diol of  = 1000 g/mol (PTMO) or poly(hexametylene carbonate)diol of  = 860 g/mol (PHCD). For all the polymers, the structure, physicochemical, thermal, and mechanical properties were determined. In addition, for selected polymers, optical properties (refractive index and transparency), adhesive properties, and antimicrobial activity were also determined. The type and amount of soft segment used for the synthesis of SPURs had a significant effect on the properties of the polymers. SPURs from PHCD are characterized by higher glass transition temperatures, molar masses, hardness (up to 91/50°Sh in scale A/D), and tensile strengths (up to 36.5 MPa) but lower elongations at break compared with the SPURs with PTMO. The tests of adhesion and optical properties showed that the PHCD‐based SPUR was characterized by higher value of refractive index, transparency, and more than three times the adhesive strength than the PTMO‐based SPUR. Antimicrobial activity studies showed that the SPUR presence in the medium inhibited proliferation of both Gram‐positive and Gram‐negative bacteria. Copyright © 2017 John Wiley & Sons, Ltd.     

Chemical structure and physical properties in polyester based segmented polyurethanes—I: Dynamic mechanical properties

Nine polyester based segmented polyurethanes and one polyurea have been synthesised, wet spun into fibres and cast into films. Both forms have been found to have melting points and densities strongly dependent on soft segment (polyester) concentration, the films having higher values in each case. Electron microscope studies have revealed the presence of crystallinity within the hard domains. Dynamic mechanical measurements showed several transitions: an α transition above 200° complete in several film samples but incomplete in fibre, an α' transition between 47 and 80° and a β transition in the region of ?20°. The α transitions occurred in the film but not in fibre, the α' transition in the fibre but not the film and the β transition in both. The significances of the transitions are discussed in terms of physical and chemical structure.     

Synthesis and ESCA surface studies of octadecyl chain-extended polyurethanes

Poly(ether urethane)s as biomaterials display certain favorable mechanical and biocompatibility properties. Earlier studies suggest that improved blood compatibility might be attained by introducing hydrocarbon groups at the surface. We synthesized and characterized a series of polyurethanes in which a N-2,3-dihydroxypropyl-N′-octadecyl urea chain extender (ODCE) was incorporated into the poly(tetramethylene glycol) (PTMO)/4,4′-methylenebis(phenylene isocyanate) (MDI) system. Molecular weights of the polymers varied between 40,000 and 250,000. An electron spectroscopy for chemical analysis (ESCA) study of the ODCE polyurethane surface revealed a substantially enhanced hydrocarbon concentration compared to a control PTMO/MDI/ethylene diamine (ED) polyurethane surface. Also, bulk composition analyses and ESCA data of the ODCE polymers indicated that the percentage of carbon was higher in the surface region than in the bulk. Thus, the ODCE polymer showed a marked increase in hard-segment concentration in the surface region compared to the bulk region and to the ED polymer.