Synthesis and properties of polyurethanes containing phosphatidylcholine analogues in the polymer backbone

New polyurethanes ( 4a, 4b ) and a segmented polyurethane ( 4c ) bearing phosphatidylcholine moieties in the main chain were synthesized. They are thermally stable up to 300°C and show the viscosity behaviour of common polyelectrolytes. Preliminary studies suggest that these polyurethanes are interesting new biomaterials.     

X-ray shielding polyurethanes: Synthesis and characterization

Synthesis and characterization of X-ray shielding thermoplastic polyurethane elastomers which are capable of blocking harmful radiation emitted by various sources are reported. X-ray shielding capability was generated in the polymer by covalently binding iodine atoms in a monomer and polymerizing it with other monomers such that the resultant polymer has the capability of shielding X-radiation. For rendering X-ray shielding capability to the polyurethane, Bisphenol-A (BPA) was iodinated to 4,4′-isopropylidinedi-(2,6-diiodophenol) (IBPA) and it was used as a chain extender during the synthesis of polyurethane. Polyurethanes were synthesized by reacting 1,6-diisocyanatohexane and IBPA with two different polyols, namely, poly(tetramethylene glycol) and poly(hexamethylene carbonate) diol. X-ray shielding polyurethanes (XPU) were characterized by infrared spectroscopy, thermogravimetry, dynamic mechanical analysis, energy-dispersive X-ray analysis, gel permeation chromatography, and X-radiography. Studies showed that by effectively changing polyol from polyether to polycarbonate, XPUs having different physicomechanical properties could be manufactured. Furthermore, these polyurethanes were also found to be noncytotoxic to L929 fibroblast cell lines. X-ray images revealed that the incorporation of IBPA has rendered X-ray opacity to the polyurethanes which are several times higher than the aluminum wedge of equivalent thickness. The materials are sufficiently flexible and rubbery, so can be used as coatings, films, or sheets for applications in energy sector, power-generating nuclear power plants, defense sector (bunkers for army personnel), medical applications (X-ray diagnostic and CT scanner rooms, gamma radiation therapy of cancer), etc.     

Synthesis and characterization of polyimides with ether linkages

Thermoplastic and thermoset polyimides derived from 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) and 4,4′-bis(4-aminophenoxy)-2,2′-dimethylbiphenyl (BAPD) were prepared and characterized. Their physical and thermal properties as well as the polyelectrolyte effect exhibited by BTDA–BAPP polyamic acids in NMP solution were discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2559–2567, 1999     

Synthesis,characterization and quantum yields of multichromic poly(azomethine)s containing carbazole unit

Poly(azomethine)s containing phosphor, silane and carbazole were synthesized with multiple stage and examined through different photophysical, electrochemical, and thermal behaviours. Following substances were synthesized as an initial step: N-hexyl-carbazole (CH) and N-hexyl-carbazolaldehyde (CHDA), via elimination reaction in argon media and N-hexyl-carbazole azomethine (CHA) via condensation reaction of CHDA with 4-aminophenol also poly(azomethine)s (P-Si-CHA, P-P-CHA) containing silane and phosphor via elimination reaction. The structures of synthesized compounds were confirmed by Fourier-transform infrared spectroscopy (FT-IR), Ultraviolet–visible spectroscopy (UV–Vis) and nuclear magnetic resonance spectroscopy (NMR). Electrochemical properties of compounds were examined with cyclic voltammetry (CV) technique. Fluorescence measurements were utilized to investigate the photochemical behaviors by photoluminescence (PL) analysis. CHA compound surprisingly presented multicolor emission behavior (when excited at 370, 420, 480, 540 and 580 nm, the solution emitted blue, green, yellow, orange and red lights, respectively) with relatively high quantum yield (19.9%) in DMF solvent. Additionally, thermal behaviors of all compounds were determined by TG and DSC techniques. Surface morphologies of polymers were imaged with scanning electron microscope (SEM).     

Synthesis and characterization of side-chain liquid crystal polyurethanes

A series of liquid crystal α-[bis(2-hydroxyethyl)amino]-ω-(4-nitroazobenzene-4′-oxy)alkanes (Cn-diol) with different alkyl chain length has been synthesized. All Cn-diols exhibit a smectic phase that has been identified by means of polarizing microscopy and differential scanning calorimetry. These compounds are suitable monomers for the synthesis of side-chain liquid crystalline polyurethanes and polyesters. They were polymerized with hexamethylene diisocyanate to corresponding SCLC polyurethanes in which the spacer length was varied from 2 to 12 methylene units. Polyurethanes (CnP) with spacer lengths n ≥ 4 exhibited liquid crystalline behavior. Fourier transform infrared temperature studies of the CnP were done focusing on H-bonds between the N H and CO groups of the urethane backbone. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2871–2888, 1997     

Microporous polyurethanes: Synthesis and investigation of the mechanism of the pore formation

A new approach for microporous polymeric material is developed utilizing the secondary interactions such as hydrogen bonding in the polymer chains in polyurethane systems at ambient conditions. A new series of highly rigid, thermally stable, and readily soluble cycloaliphatic polyurethanes were designed and synthesized for this purpose, based on new tricyclodecanedimethanol and 1,4‐cyclohexanedimethanol. The hydrogen‐bonding interactions induce phase separation in solution, which leads to polymer‐rich and solvent‐rich domains; subsequent evaporation of the solvent molecules results in micropores. The phase‐separation process in the polyurethane is found to be highly dependent on the chemical structures of the polymer chain backbone. ¹H NMR titration experiments were carried out to understand the mechanism of the micropore formation and its dependence on different structural subunits. The hydrogen‐bonding association constant (K) obtained from the titration experiments revealed that higher the K‐value more the tendency to form micropores. A fully cycloaliphatic polyurethane produces micropores of sizes ranging from 1 to 8 μm, and each pore is separated by 10^?20 μm, whereas the replacement of one of the cyclic unit in the backbone disturbs the entire phase‐separation process and results in nonporous morphology. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1296–1308, 2006     

Synthesis and thermal properties of bisphthalonitriles containing aromatic ether nitrile linkages

Low-melting bisphthalonitrile oligomers with variable length of aromatic ether nitrile linkages (nPEN-BAPh) was firstly synthesized and the length of the linkages (n) was controlled by mole ratio of 2, 6-dichlorobenzonitrile and bisphenol A. The oligomers were characterized by FTIR and NMR spectra, and detailed study showed that the linkages were constructed in the backbone of nPEN-BAPh. The FTIR showed, with the curing reaction progressed, the characteristic peak of nitrile at 2230 cm⁻¹ disappeared while the characteristic peak of phthalocyanine ring at 3290, 1010 cm⁻¹ and triazine ring at 1360 cm⁻¹ appeared. The melting and polymerization temperature of the oligomers was around 60 °C and 220 °C, respectively. So a large processing window was obtained. The char yields of completely cured materials were above 65% at 800 °C in nitrogen and over 70% at 600 °C in air. All materials exhibited excellent thermal and thermo-oxidative stability.     

Novel long chain unsaturated diisocyanate from fatty acid: Synthesis,characterization, and application in bio‐based polyurethane

A novel long chain linear unsaturated terminal diisocyanate, 1,16‐diisocyanatohexadec‐8‐ene (HDEDI) was synthesized from oleic acid via Curtius rearrangement. Its chemical structure was identified by FTIR, ¹H NMR, ¹³C NMR, and HRMS. This diisocyanate was used as a starting material for the preparation of entirely bio‐based polyurethanes (PUs) by reacting it with canola diol and canola polyol, respectively. The physical properties and crystalline structure of the PUs prepared from this diisocyanate were compared to their counterparts prepared from similar fatty acid‐derived diisocyanate, 1,7‐heptamethylene diisocyanate (HPMDI). The HDEDI based PUs demonstrated various different properties compared to those of HPMDI based PUs. For example, HDEDI based PUs exhibited a triclinic crystal form; whereas HPMDI based PUs exhibited a hexagonal crystal lattice. In addition, canola polyol‐HDEDI PU demonstrated a higher tensile strength at break than that of canola polyol‐HPMDI, attributed to the higher degree of hydrogen bonding associated with the former sample. Nevertheless, lower Young's modulus and higher elongation in canola polyol‐HDEDI PU were obtained because of the flexibility of the long chain introduced by the HDEDI diisocyanate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3302–3310, 2010     

Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources

Oligomeric polyether polyols were obtained through the acid‐catalyzed ring‐opening polymerization of epoxidized methyl oleate and the subsequent partial reduction of ester groups to give primary alcohols. The oligomers were characterized with titration, spectroscopic techniques (Fourier transform infrared and nuclear magnetic resonance), matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, size exclusion chromatography, and differential scanning calorimetry. Depending on the degree of reduction, polyols of different hydroxyl content values were obtained and were reacted with 4,4′‐methylenebis(phenyl isocyanate) to yield polyurethanes. These materials, which were characterized by differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis, could behave as hard rubbers or rigid plastics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 634–645, 2006     

Synthesis and characterization of a multiarm star polymer

A multiarm star polymer was synthesized through the grafting of oligo polyglycol with urethane chain end units onto the core of hyperbranched polyglycerol (HPG), which was obtained through the cationic ring‐opening polymerization of glycidol. Samples were characterized with ¹³C NMR, liquid chromatography/mass spectrometry, vapor pressure osmometry, and Raman spectroscopy. The degree of branching of HPG was 0.54, and the number of arms grafting onto HPG was 4. The urethane of the arms mainly reacted with the terminal hydroxy groups of HPG. The differences between the spin–spin relaxation times indicated that the terminal segments of the star were more flexible than those of the core. Grafting polyglycol polyurethane (soft segments of polyurethane is polyglycol) onto HPG improved its dimensional stability. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2356–2364, 2004     

Synthesis and characterization of new poly(azomethine ester)s having phenylthiourea units

New polyesters having azomethine and phenylthiourea groups in the polymer backbone were synthesized by interfacial polycondensation method. The dihydroxy monomer N-(4-hydroxy-3-methoxybenzal) N′-(4′-hydroxyphenyl)thiourea was condensed with six diacid chlorides: terephthaloyl, isophthaloyl, azeloyl, suberoyl, pimeloyl and adipolyl chlorides. The resulting polyesters were characterized by viscosity, IR, NMR and TGA analysis. The wholly aromatic poly(azomethine ester) derived from terephthaloyl chloride when blended with polyaniline/NH₄OH, polyaniline/HCl and pure polyaniline shows conductance in the range 3.2 × 10⁻³-0.91 × 10⁻¹ S cm⁻¹.     

Synthesis and characterization of new polyimides containing calix[4]arenes in the polymer backbone

Two diaminocalix[4]arene monomers were synthesized from p-tert-butylcalix[4]arene through a 4-step reaction sequence. New copoly(amic acid)s containing calix[4]arene moieties on the polymer backbone were successfully synthesized in N-methyl-2-pyrrolidone by polycondensations of 4,4′-oxydiphthalic anhydride (ODPA) with the diaminocalix[4]arene monomers using 4,4′-oxydiphenylene diamine (ODA) as a comonomer. These copoly(amic acid)s were soluble in aprotic polar solvents, so that they can be processed in various ways. The copoly(amic acid) precursors were thermally converted to the corresponding copolyimides in films. The copolyimide films are amorphous, but insoluble in common solvents. They are thermally stable up to 366°C. The copolyimides exhibit relatively high TEC's, low T_g's, low refractive index, low dielectric constant, low optical anisotropy, low dielectric anisotropy, and low water uptake, compared to those of conventional ODPA-ODA polyimide. These property characteristics were interpreted in regard to bulky, cone-like calix[4]arene moieties and their effects on the chain conformation and morphological structure. The processability and property characteristics support that both of the copolyimides containing calix[4]arene moieties are potential candidate materials suitable for membranes, antioxidant additives, chemical sensor devices, and microelectronic devices. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2013–2026, 1999     

Synthesis of novel cationic lipids with fully or partially non-scissile linkages between the hydrocarbon chains and pseudoglyceryl backbone

Five novel cationic lipids with fully or partiallynon-scissile linkage regions between the pseudoglyceryl backbone and the hydrocarbon chains have been synthesized. The membrane-forming properties of these new lipids are briefly presented.     

Synthesis and properties of novel optically active polyimides

A facile synthesis of an optically active di‐isocyanate containing alkylene groups and a preformed imide structure is described. Polycondensation reactions of the prepared di‐isocyanate with pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and hexafluoroisopropylidene diphthalic anhydride resulted in the preparation of optically active, thermally stable polyimides. The prepared monomer and polymers were characterized by conventional methods. Optical and physical properties of the polymers including thermal stability, thermal behavior, solution viscosity, and solubility behavior were studied. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 514–518, 2001     

Polyurethanes containing sulfur. I. New thermoplastic polyurethanes with benzophenone unit in their structure

New thermoplastic nonsegmented thiopolyurethanes were obtained from the low-melting aliphatic–aromatic thiodiols 4,4′-bis(2-hydroxyethylthiomethyl)benzophenone (BHEB), 4,4′-bis(3-hydroxypropylthiomethyl)benzophenone (BHPB), and 4,4′-bis(6-hydroxyhexylthiomethyl)benzenophenone(BHHB) as well as hexamethylene diisocyanate (HDI), both by melt and solution polymerization with dibutyltin dilaurate as the catalyst. The effect of various solvents on molecular-weight values was examined. The polymers with the highest reduced viscosities (0.63–0.88 dL/g) were obtained when the polymerization was carried out in a solution of tetrachloroethane, N,N-dimethylacetamide, and N,N-dimethylacetamide or N,N-dimethylformamide for BHEB-, BHPB-, and BHHB-derived polyurethanes, respectively. These polymers with a partially crystalline structure showed glass-transition temperatures (T_g) in the range of −1 to 39 °C, melting temperatures (T_m) in the range of 107 to 124 °C, and thermal stabilities up to 230 to 240 °C. The BHEB-derived polyurethane is a low-elasticity material with high tensile strength (ca. 50 MPa), whereas the BHPB- and BHHB-derived polyurethanes are more elastic, showing yield stress at approximately 16 MPa. We also obtained segmented polyurethanes by using BHHB, HDI, and 20 to 80 mol % poly(oxytetramethylene) glycol (PTMG) of M̄_n = 1000 as the soft segment. These are high-molecular thermoplastic elastomers that show a partially crystalline structure. Thermal properties were investigated by thermogravimetric analysis and differential scanning calorimetry. The increase in PTMG content decreases the definite T_g and increases the solubility of the polymers. These segmented polyurethanes exhibit the definite T_g (−67 to −62 °C) nearly independent of the hard-segment content up to approximately 50 wt %, indicating the existence of mainly phase-separated soft and hard segments. Shore A/D hardness and tensile properties were also determined. As the PTMG content increases, the hardness, modulus of elasticity, and tensile strength decrease, whereas elongation at break increases. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4140–4150, 1999     

Synthesis,structural characterization,and properties of polyurethane elastomers containing various degrees of unsaturation in the chain extenders

We prepared polyurethane block copolymers with both 50 and 70% soft segment concentrations, using 4,4′‐diphenylmethane diisocyanate–poly(propylene glycol) prepolymer and 1,4‐butanediol, cis‐2‐butene‐1,4‐diol, and 2‐butyne‐1,4‐diol as chain extenders. The effects of the different chain extenders were observed during synthesis and in the final products. A comparison of spectroscopic, mechanical, and thermal data reveals that polymer properties can be significantly altered by differences in chemical bonding within the chain extender backbone. Although all data support the expected differences in phase morphology between the two series of samples, they also suggest that increasing chain extender unsaturation reduced reactivity with isocyanate, adversely affected hydrogen bonding, lowered the degree of crystallinity of the hard segments, and decreased phase separation. The tensile strength, elongation, modulus, and elastic recovery decreased and the electrical conductivity of iodine‐doped samples increased with increasing chain extender unsaturation. The thermal stability of the urethane group was also lower in samples with increased unsaturation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1316–1333, 2002     

Synthesis and characterization of new polyimides containing ethynylene linkages

We have synthesized a series of new diamines containing bis(ethynylaniline) linkages by bromine substitution reaction of ethynylaniline with 4,4′-bis(4-bromophthalimido)diphenylether (PODA) or 1,4-bis(4-bromophthalimido)benzene (PPDA). The intermediates were separated at each step, purified and characterized by the spectroscopic techniques. The model compound having imide and triple bond moiety was synthesized in order to elucidate the nature of the products formed from the ethynyl curing by FT-IR spectroscopy. The polymerization reaction of ethynylaniline diamines with various dianhydrides gave fully imidized and soluble aromatic polyimides. The thermally cured polyimide samples displayed good solvent resistance. The thermal crosslinking of triple bond moieties in the main chain was carried out by heating in the temperature range from 150 to 400 °C. The glass transition temperature of polyimide completely disappeared after heat treatment at 400 °C for 5 min. The polyimides derived from diamines containing bis(ethynylaniline) groups were thermally stable after heat treatment.     

Synthesis and characterization of bismaleimides derived from polyurethanes

A series of novel bismaleimides (BMIs) were prepared from maleic anhydride and polyurethane prepolymers based on MDI (4,4′-diphenylmethane diisocyanate) and polyether and polyester diols with various chain lengths. All the BMIs were characterized by IR, ¹H-NMR, and elemental analysis. DSC studies indicated that the thermal polymerization of the BMIs could be carried out in the temperature range of 102–245°C, and that curing behavior was significantly affected by the molecular weight of the BMIs. The crosslinked BMI elastomers showed good mechanical properties and much better thermal stability than that of the traditional polyurethane elastomers. The glass transition temperatures, mechanical, and dynamic mechanical properties were dependent on the types of polyols used and the resultant crosslink densities due to various chain lengths of the BMIs. © 1994 John Wiley & Sons, Inc.