Synthesis and nonlinear optical properties of polyurethanes containing nitro-substituted 1,3,4-oxadiazole chromophores

NLO active nitro-substituted oxadiazole chromophores were prepared and condensed with tolylene-2,4-diisocyanate (TDI) and 4,4′-methylenedi(phenyl isocyanate) (MDI) to yield a series of polyurethanes. The resulting polyurethanes exhibited an excellent solubility in many common organic solvents, suggesting that these polyurethanes offer good processability. Molecular structural characterization of these polyurethanes was achieved by FT-IR, UV–vis, ¹H NMR and analytical technique. The weight-average molecular weights of polyurethanes determined by gel permeation chromatography (GPC) were in range of 21,000–23,000 (M_w/M_n = 1.87–2.00). Thermal behavior of polyurethanes was investigated using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The glass transition temperatures of the polyurethanes were in the range of 155–170 °C. The second harmonic generation (SHG) coefficients (d₃₃) of the poled polyurethanes were in the range of 38.93–48.64 pm/V at 532 nm. High thermal endurance of poled dipoles was observed for all the polyurethanes. Further, it was found that all the developed polyurethanes were stable up to 140 °C, signifying the acceptability for nonlinear optical devices.     

Relationship between nanoscale deformation processes and elastic behavior of polyurethane elastomers

The cyclic deformation of two polyurethane elastomers that differed in soft segment content and molecular weight was investigated. The microphase-separated morphology of the polyurethane with higher soft segment content consisted of hard segment domains dispersed in a soft segment matrix. In the polyurethane with lower soft segment content, the hard segment domains appeared to be partially cocontinuous. Following an initial ‘conditioning’ cycle, both polyurethanes exhibited reversible elastomeric behavior. Structural changes that occurred during conditioning were investigated using atomic force microscopy and Fourier transform infrared dichroism. The results provided the basis of a structural model for the deformation behavior. Yielding and reorganization of hard domains resulted in a highly oriented microfibrous morphology. Subsequent unloading and reloading were associated with reversible relaxation and reformation of the microfibrous entities. The elastic behavior of the conditioned polyurethanes was satisfactorily described by classical rubber theory with inextensibility. The structural model proposed here extended previous efforts to describe the deformation processes of polyurethanes during cyclic loading.     

Synthesis of MDI and PCL-diol-based polyurethanes containing [2] and [3]rotaxanes and their properties

We have successfully synthesized novel polyurethanes where PU1 contains a [3]rotaxane that consists of N-3,5-di-tert-butylbenzyl-N-3-hydroxypropylammonium hexafluorophosphate (AOH1) and N,N′-Dimethyl-N,N′-bis(dibenzo-24-crown-8)-terephthalamide (BisC) as well as PU2 contains a [2]rotaxane that consists of AOH1 and dibenzo-24-crown-8 ether. Diphenylmethanediisocyanate (MDI), 1,4-butanediol (BD) and poly(ε-caprolactone)diol (PCL) were used as an isocyanate, chain expander, and soft segment, respectively. A polyurethane without any rotaxane structures (PU0) were also prepared as a reference polymer. The existence of the rotaxanes in the polyurethanes was confirmed by ¹H NMR spectroscopy and TGA measurement. ATR-FT-IR spectral measurement revealed that the rotaxanes disturb the formation of hydrogen bonding between the polyurethane chains. From the DSC result, the rotaxanes retard the recrystallization of the PCL unit whereas no influence on the glass transition temperatures of the polyurethanes was observed. The retarding effect appeared remarkably with PU1. These thermal behaviors of the polyurethanes were also supported by viscoelastic measurement. In tensile test, the tensile strength and break of strain of PU1 were larger than those of PU2.     

Ring opening polymerization of 3-semifluoro- and 3-bromomethyloxetanes to poly(2,2-substituted-1,3-propylene oxide) telechelics for soft blocks in polyurethanes

The synthesis of hydroxy-terminated poly(2,2-substituted-1,3-propylene oxide) polyoxetane telechelics and co-telechelics bearing semifluorinated (-CH₂OCH₂(CF₂)_nCF₃) and functional bromomethyl pendant groups is reported. Characterization utilized ¹H NMR spectroscopy, temperature modulated DSC (MDCS), and gel permeation chromatography (GPC). Analysis of relative reactivity ratios for a 1:1 3FOx to BrOx feed indicates that in the early stages of reaction BrOx-BrOx dyad mole fraction is below the statistically predicted amount. However, a model suggests that the final telechelic dyad composition at complete reaction is not very different from a statistical copolymer. The co-telechelics have low T_gs (−33 to −39 °C) and molecular weight in a desirable range (M_w≈3-5 k). Telechelics were incorporated in polyurethanes (PUs) with isophorone diisocyanate (IPDI) and butanediol (BD) as the hard block. Characterization of polyurethane composition and bulk properties by ¹H NMR, MDSC, and GPC is described. The new polyurethanes hold promise for a ‘reaction on polymer’ approach to polyurethanes with functional soft blocks.     

Combinatorial approach to study the effect of acrylic polyol composition on the properties of crosslinked siloxane-polyurethane fouling-release coatings

The effect of acrylic polyol composition on the properties of crosslinked siloxane-polyurethane coatings was explored. An acrylic polyol library was synthesized using batch solution polymerization and characterized using high-throughput gel permeation chromatography (Rapid-GPC) and differential scanning calorimetry (DSC). Siloxane-polyurethane coatings were prepared from 3-aminopropyl-terminated poly(dimethylsiloxane) (PDMS), the acrylic polyols and a polyisocyanate crosslinker. The siloxane-acrylic-polyurethane coatings were tested for mechanical and physical properties. The siloxane-polyurethane coatings had a systematic variation in glass transition temperature and had water contact angles ranging from 95° to 100°. Many of the coatings also showed a low-force of release in the pseudo-barnacle pull-off adhesion test. Performance testing of the fouling-release properties of the siloxane-polyurethane coatings on array panels with algae, namely the diatom Navicula and sporelings (young plants) of the green seaweed Ulva was also conducted. Presented at the 2006 FutureCoat! conference, sponsored by the Federation of Societies for Coatings Technology, in New Orleans, LA, on November 1–3, 2006.     

High throughput combinatorial characterization of thermosetting siloxane–urethane coatings having spontaneously formed microtopographical surfaces

High throughput combinatorial characterization was performed on thermosetting siloxane–urethane coatings in order to find a correlation between the characterization techniques, surface topography, and adhesion strength of barnacles. A series of coatings having microtopographical surfaces with different domain sizes were prepared based on a thermosetting siloxane–urethane system. This microtopography was formed spontaneously during the film-formation process. These surfaces were characterized by atomic force microscopy (AFM), surface energy, dynamic contact angle, and pseudo barnacle pull-off adhesion and were compared to pure polyurethane (PU) and silicone rubber control. Surface energy and dynamic contact angles were measured by an automated surface energy measurement system and pull-off adhesion values were obtained from a high throughput pull-off adhesion measurement unit. The results were compared with the adhesion strength of barnacles. Presented at the 2006 FutureCoat! conference, sponsored by the Federation of Societies for Coatings Technology, in New Orleans, LA, on November 1–3, 2006.     

Plant oil polyol based poly (ester urethane) metallohybrid coatings

Research efforts are being focused to develop polymers from bioresources such as plant oils from ecological and economical viewpoints, both in academic research and chemical industry worldwide. Plant oil polymers, their organic-inorganic hybrids and composites find versatile applications today. In the present work, we have reported the preparation and characterization of linseed oil based poly (ester urethane) metallohybrids [PEUMH] from linseed oil polyol [LPO], phthalic anhydride [PAN], toluylene-2,4-diisocyanate [TDI] as organic and copper (II) acetate [Cu-Ac] (in different amount) as inorganic precursors, respectively, in “one-pot, multi-step” reaction. PEUMH were characterized by spectral, physico-chemical, thermal (TGA and DSC) and morphological analyses by standard methods. The potentiality of the same as promising coating material was also evaluated. PEUMH are foreseen as prospective candidates for application as antibacterial self-sterilizing protective coatings due to oligodynamic effect of metal.     

Synthesis, formulation, and characterization of siloxane–polyurethane coatings for underwater marine applications using combinatorial high-throughput experimentation

Crosslinked siloxane–polyurethane coatings were designed, synthesized, formulated, applied, and characterized using combinatorial high-throughput experimentation and eight coatings were selected as candidates for further characterization. First, 72 novel hydroxyalkyl carbamate and dihydroxyalkyl carbamate-terminated poly(dimethylsiloxane) (PDMS) oligomers and their carbamate-linked block copolymers with poly(ε-caprolactone) (PCL) were synthesized using a high-throughput synthesis system. These PDMS oligomers and block copolymers were characterized for their molecular weight using high-throughput Gel Permeation Chromatography (Rapid-GPC). The 72 oligomers were then incorporated into siloxane–polyurethane formulations at four different levels resulting in 288 coatings. After initial screening of these 288 coatings, eight coatings were selected for further characterization. Differential scanning calorimetry, dynamic mechanical analysis, X-ray photoelectron spectroscopy and surface energy analysis demonstrate the presence of PDMS on the surface with a polyurethane underlayer. Pseudo-barnacle adhesion and the attachment strength of reattached live barnacles (Balanus amphitrite) were in good agreement. Out of the eight coatings that were down-selected, two coatings performed well in algal (Ulva), bacterial (Cytophaga lytica, Halomonas pacifica), and barnacle (Balanus amphitrite) laboratory screening assays and are potential candidates for ocean testing. This paper was awarded Second Place in the 2006 Roon Awards competition, held as part of the FutureCoat! conference, sponsored by the Federation of Societies for Coatings Technology, in New Orleans, LA, on November 1-3, 2006.     

Synthesis and properties of shape memory polyurethanes generated from schiff-base chain extender containing benzoyl and pyridyl rings

In this study, 4,4′-diphenylmethane diisocyanate and polytetramethylene glycol were used to prepare a prepolymer; N,N′-bis(4-hydroxybenzylidene)-2,6-diaminopyridine (BHBP) was used as a chain extender; and these elements were combined to prepare a novel polyurethane, BHBP/PU. Gel permeation chromatography revealed that the molecular weight of the BHBP/PU samples increased as the BHBP content was increased. Fourier transform infrared spectroscopy demonstrated that high BHBP content facilitated strong hydrogen bonding in the samples. Differential thermogravimetry indicated that the initial decomposition temperature of BHBP/PU-3 was approximately 10 °C higher than that of BHBP/PU-1. Differential scanning calorimetry and dynamic mechanical analysis revealed that increasing the BHBP content substantially increased both the glass transition and dynamic glass transition temperatures of the BHBP/PU samples. The tensile strengths of BHBP/PU-1, BHBP/PU-2, and BHBP/PU-3 were 7.7, 10.9, and 21.6 MPa, respectively, with corresponding Young’s moduli of 0.7, 1.9, and 3.3 MPa. These results demonstrated that both the tensile strength and Young’s modulus of the BHBP/PU samples increased as the BHBP content was increased. Moreover, the BHBP/PU samples exhibited excellent shape recovery of >90%.     

Fast-curing polyurethane adhesives derived from environmentally friendly hyperbranched polyglycerols - The effect of macromonomer structure

Transformation of glycerol to hyperbranched polyglycerols (HBPGs) and their further application as macromonomers for fast-curing polyurethane adhesives were described. An approach allowing for using of hyperbranched polyglycerols derived from renewable glycerol in adhesive technology was investigated. Four hyperbranched polyglycerols of different structures and functionalities were synthesized and crosslinked with polymeric methylenediphenyldiisocyanate (pMDI) and hexamethylenediisocyanate (HDI). Macromolecule functionality and functional group distribution were shown to be a critical factor in terms of the adhesive performance. The studied approach allowed to conclude that environmentally friendly polyglycerols - derived from renewable glycerol - when properly designed could successfully replace petroleum-based ones.