Combining cationic ring‐opening polymerization and click chemistry for the design of functionalized polyurethanes

A straightforward strategy for the synthesis and functionalization of polyurethanes (PUs) via the use of alkyne‐functionalized polytetrahydrofuran (PTHF) diols is described. The alkyne groups have been introduced into the PTHF chains by the cationic ring‐opening copolymerization of tetrahydrofuran and glycidyl propargyl ether. These PTHF prepolymers were combined with 1,4‐butanediol and hexamethylene diisocyanate for the synthesis of linear PUs with latent functionalization sites. The polyether segments of the PUs have then been coupled with several types of functionalized azides by the copper‐catalyzed azide‐alkyne “click” chemistry, for example with phosphonium containing azides for their antibacterial properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Thermal and pH responsive high molecular weight poly(urethane‐amine) with high urethane content

Aliphatic poly(urethane‐amine) (PUA) was synthesized from copolymerization of CO₂ and 2‐methylaziridine (MAZ) using Y(CCl₃COO)₃‐ZnEt₂‐glycerine coordination catalyst, the urethane content of PUA was over 80%, and its yield could reach 90%. PUA with molecular weight as high as 31.0 kg/mol was obtained when the copolymerization reaction was carried out in N,N‐dimethylacetamide (DMAc), mainly due to the good solubility of PUA in DMAc. PUA exhibited reversible thermo‐responsive property in deionized water, and the lower critical solution temperature (LCST) was highly sensitive to its urethane content and molecular weight, which was observed in a broad window from 37 to 90 °C. Furthermore, the phase transition behavior could also be controlled by change of pH value. When the pH value of the PUA aqueous solution changed from 9.2 to 13, the LCST value of the solution decreased from 48.4 °C to 30 °C. Therefore, the PUA showed thermo‐ and pH‐ dual responsive performance in water. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

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     

Morphology and physical properties of a novel Ramie‐PU blended nonwoven by electrospinning: The effect of cosolvent ratio

A novel macro/nano blended nonwoven with excellent physical properties was prepared by electrospinning polyurethane (PU) nanofibers onto the surface of ramie webs under different weight ratios of N,N‐dimethylacetamide (DMAc)/acetone cosolvents. The ratio of cosolvents has a significant influence on the morphology, tensile properties, resilience, and thermal properties of the resultant samples. Bead‐free and fine interconnected nanofibers were obtained with an increase of acetone content up to 60 wt%. The total physical properties of the blended nonwovens were optimal for a DMAc/acetone ratio of 40/60, in which the tensile load at break, extension at break and Young's modulus were 441, 54, and 256% higher than that of pure ramie web, respectively. The resilience of the blended nonwovens was ～20% higher than that of nonblended ramie web. The significant improvement of physical properties may be due to the good connection between PU nanofiber membranes and ramie webs and the molecular chain structure differences, interconnected structural differences, and high extensibility of PU nanofibers, according to the results of crystallization by differential scanning calorimetry (DSC) and morphological observation by scanning electronic microscopy (SEM). © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1–14, 2010     

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.     

Easily grafted polyurethanes with reactive main chain functional groups. Synthesis,characterization, and antithrombogenicity of poly(ethylene glycol)-grafted poly(urethanes)

A novel synthesis of poly(ethylene glycol) (PEG)-grafted poly(urethanes) (PURs) is described based on a precursor PUR containing free amino groups in the main chain. Three different poly(urethane) backbones were prepared: a homopoly(urethane) comprised of N-Bocdiethanolamine (BDA) and 4,4′-methylenebis(phenyl isocyanate) (MDI), a copoly(urethane) (COPUR) consisting of BDA, N-benzyldiethanolamine and MDI, and a poly(urethane urea) (PUU) that was prepared from BDA, MDI, and ethylenediamine as the chain extender. The M_n of these poly(urethanes) ranged from 32,000 to 72,000 g/mol. PEG (750, 1,900, and 5,000 g/mol) was grafted onto the boc-deprotected poly(urethanes) via the chloroformate. Films of the polymers were spin cast from dilute solutions, annealed, and the surfaces analyzed by goniometry. Water contact angle data indicates increasing PEG surface coverage of the poly(urethanes) with increasing PEG molecular weight. Reorientation of the polymer films is evidenced by contact angle hysteresis. Polymer thrombogenicity, which was studied using blood perfusion experiments, shows that COPUR-g-PEG5000 and PUU-g-PEG5000 exhibit very little platelet adhesion. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3441–3448, 1999     

Segmented Polyurethanes for Medical Applications: Synthesis,Characterization and in vitro Enzymatic Degradation Studies

Degradable segmented poly(ether-ester-urethanes) of variable segment chemistry and content were synthesized and characterized. Polycaprolactone diol, a series of poly(ether-ester) block copolymers, and a diisocyanate giving non toxic degradation products were used to form the prepolymer. Cyclohexane dimethanol and a L–phenylalanine–based diester (Phe diester) were used as chain extenders. The influence of α-chimotrypsin on the degradation was investigated by exposing the polymers to buffer and enzyme solutions for 12 days. The SEM, SEC, and gravimetric results showed that a significant erosion of the Phe diester containing polymer compared with the control polyurethane occurred in the presence of the enzyme but not in a normal buffer solution.     

Clickable polyurethanes based on s‐triazine ring containing aromatic diisocyanate bearing pendent alkyne group: Synthesis and postmodification

A new s‐triazine ring containing aromatic diisocyanate bearing a pendent alkyne group, namely, 2,4‐bis(4‐isocyanatophenoxy)?6‐(prop‐2‐yn‐1‐yloxy)?1,3,5‐triazine was synthesized and reacted with various diols viz., 1,10‐decanediol, tetraethylene glycol and polyethylene glycols in the presence of dibutyltin dilaurate as the catalyst to obtain a series of linear polyurethanes. The selected polyurethanes possessing pendent alkyne groups were postmodified with chemically diverse azides viz., 1‐(azidomethyl)benzene, 1‐(azidomethyl)pyrene, and methoxy end‐caped poly(ethylene glycol) azide via copper‐catalysed azide‐alkyne Huisgen 1,3‐dipolar cycloaddition. FTIR and ¹H NMR spectra indicated quantitative click reaction. UV–vis and fluorescence spectroscopic analysis confirmed complete incorporation of pyrenyl groups indicating the formation of fluorescence active polyurethane by postmodification with 1‐(azidomethyl)pyrene. TG analysis of polyurethanes indicated two stage weight loss and their thermal stability, as judged by T ₁₀ values, was governed by weight percent of urethane linkages. The water contact angle measurements revealed improved wettability with increased content of PEG either in the backbone of polyurethanes or as grafted chains. DLS and TEM studies confirmed that certain polyurethanes possessing PEG segments displayed self‐assembly in aqueous solution, which was further supported by pyrene encapsulation studies using UV–vis spectroscopy. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1008–1020     

Biobased polyurethanes from polyether polyols obtained by ionic‐coordinative polymerization of epoxidized methyl oleate

A series of poly(ether urethane) networks were synthesized from polyether polyols obtained by ionic‐coordinative polymerization of epoxidized methyl oleate (EMO) using 4,4′‐methylenebis(phenyl isocyanate) or l ‐lysine diisocyanate as coupling agents. Moreover, a variety of segmented poly(ether urethane) networks with different hard segment contents were obtained using 1,3‐propanediol as the chain extender. The materials were characterized by differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical thermal analysis, and tensile properties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Aggregation structure and mechanical properties of functionally graded polyurethane elastomers

Functionally graded polyurethane elastomers (FGPUEs) were prepared with two molds fixed at different temperatures (30 and 150 °C). The effects of the molar ratio of the curing agent (60/40, 75/25, or 97/3 1,4‐butane diol/1,1,1‐trimethylol propane) and the molecular weight of the polymer glycol (number‐average molecular weight = 2000 or 3000) on the molecular aggregation state and mechanical properties of the FGPUEs were investigated with differential scanning calorimetry, polarized optical microscopy, dynamic viscoelastic measurements, and tensile tests. The aggregation state of the FGPUEs was changed continuously from the one side (lower temperature side) to the other side (higher temperature side); for example, the glass‐transition temperature gradually increased in this direction. Also, the number of spherulites formed in the FGPUEs increased in the same manner. In the mechanical tests, the tensile strength and elongation at break of the lower temperature side were higher than those of the higher temperature side. This was correlated with the strong phase separation of the lower temperature side. The poly(oxytetramethylene glycol)‐based FGPUE with a chain extender of 75 wt % showed the largest degree of the temperature gradient. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2355–2363, 2003