Cycloaliphatic Diisocyanate Research Articles

Poly(Siloxane–Propylene Oxide–Urethane–Ureas) Based on Cycloaliphatic Diisocyanates: Synthesis and Properties

New network poly(siloxane–propylene oxide–urethane–ureas) based on α,ω-bis[(3-aminopropyl)diethoxy]oligodimethylsiloxanes, oligo(propylene oxide), and cycloaliphatic diisocyanates are synthesized. The resulting polymers are studied by differential scanning calorimetry and thermogravimetric analysis; their stress–strain characteristics are elucidated. These polymers are found to feature microphase separation and, consequently, two glass transition temperatures, defined by the chemical structures of the microphases. It is shown that an increase in the molecular weight and mass content of siloxane blocks leads to a decrease in the elastic modulus and tensile strength.

Simple and Efficient Synthesis of Oligoetherdiamines: Hardeners of Epoxyurethane Oligomers for Obtaining Coatings with Shape Memory Effect.

In this work, new polymers with a shape memory effect for self-healing coatings based on oligomers with terminal epoxy groups, synthesized from oligotetramethylene oxide dioles of various molecular weights, were developed. For this purpose, a simple and efficient method for the synthesis of oligoetherdiamines with a high yield of the product, close to 94%, was developed. Oligodiol was treated with acrylic acid in the presence of a catalyst, followed by the reaction of the reaction product with aminoethylpiperazine. This synthetic route can easily be upscaled. The resulting products can be used as hardeners for oligomers with terminal epoxy groups synthesized from cyclic and cycloaliphatic diisocyanates. The effect of the molecular weight of newly synthesized diamines on the thermal and mechanical properties of urethane-containing polymers has been studied. Elastomers synthesized from isophorone diisocyanate showed excellent shape fixity and shape recovery ratios of >95% and >94%, respectively.

Mathematical modeling and experimental study of mechanical properties of chitosan based polyurethanes: Effect of diisocyanate nature by mixture design approach

This research work has been done to investigate the influence of the geometry of aliphatic diisocyanate (hexamethylene diisocyanate, HDI), cycloaliphatic diisocyanate (isophorone diisocyanate, IPDI) and aromatic diisocyanate (2,4-toluene diisocyanate, TDI) on the tensile strength and hardness of chitosan based polyurethane biomaterials. For this purpose, chitosan (CS) and polycaprolactone diol (PCL) based polyurethanes have been synthesized with above mentioned diisocyanates following statistical design (mixture design). Simplex mixture design was used for analysis and totally 10 experiments were generated by the software. Samples were tested based on the portions of mixture components. Fourier transform Infrared attenuated total reflection (FTIR-ATR) and nuclear magnetic resonance (NMR) spectroscopic techniques confirmed the synthesis of chitosan based polyurethanes. This biomaterial has been established as an innovative and promising strategy to improve the mechanical strength of chitosan-based polyurethanes.

Thermal and Mechanical Behavior of New Transparent Thermoplastic Polyurethane Elastomers Derived from Cycloaliphatic Diisocyanate.

New transparent thermoplastic polyurethane elastomers (TPURs) with the hard-segment content of ≈50 mass % were synthesized by one-step melt polyaddition of 1,1′-methanediylbis(4-isocyanatocyclohexane), 2,2′-methylenebis[(4,1-phenylene)-methylenesulfanediyl]diethanol (diol E), 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid (DMPA), a poly(oxytetramethylene) diol of = 1000 g/mol (PTMO), or a poly(hexametylene carbonate) diol of = 860 g/mol (PHCD). Herein, I prepared TPURs in which 20, 40, and 60 mol % of diol E was replaced with DMPA, an ionic chain extender. The structure of polymers was examined by ATR-FTIR. Their thermal and mechanical behaviors were determined by means of thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), tensile tests, and Shore A/D hardness. Their optical properties are described. Generally, the addition of carboxyl groups to the polymer resulted in decreases in their thermal stability, transparency, and refractive indexes. Furthermore, the use of different soft segments revealed significant differences in both mechanical and thermal properties of the polymers obtained.

Development of Novel Polyurethanes with High Elasticity and Durability Based on a Cycloaliphatic Diisocyanate Controlled the Stereoisomer Structure

Development of Novel Polyurethanes with High Elasticity and Durability Based on a Cycloaliphatic Diisocyanate Controlled the Stereoisomer Structure

Preliminary study on bio-based polyurethane adhesive/aluminum laminated composites for automotive applications

Composite materials that are offered for real applications in the automotive industry vary from thermoplastics to laminated structures. This study focuses on a preliminary study on the processing and characterization of bio-based polyurethane (PU) adhesive/aluminum-laminated composites. Five different formulations of PU adhesives were prepared from five different formulations of polycaprolactone (PCL) polyols. The PCL polyols were synthesized by a ring opening polymerization of ɛ-caprolactone initiated by a blend of palm kernel oil polyesteramide (PPKO) and 1,6-hexanediol (HDO) with various weight ratios of PPKO:HDO (0:100, 25:75, 50:50, 75:25, and 100:0). The PCL polyols were reacted with a mixture of aromatic and cycloaliphatic diisocyanate. Physical and chemical analyses of PCL polyols such as viscosity, OH number, molecular weight, and proton nuclear magnetic resonance (1H-NMR) were carried out. The swelling and mechanical testing were performed to explore the correlation between the structure of PU network and its properties. The adhesion strength of bio-based PU/aluminum-laminated composites was found to be influenced by the structure of the PU network system. The ratio of 75:25 (PPKO:HDO) was found to be the optimum based on the mechanical strength of laminated composites and the thermal stability of the PU adhesive.

Fluorinated Polyurethanes, Synthesis and Properties.

Fluorinated polyurethanes with a glass transition temperature as low as −139 °C and a decomposition onset temperature of 247–330 °C were prepared by a reaction of fluorinated alcohols with aromatic and cycloaliphatic diisocyanates in solution or melt.

Effect of surface treatments on the durability of green polyurethane adhesive bonded aluminium alloy

Surface treatment of aluminium alloy plays a significant role in improving the strength of the adhesive bond. In this study, an aluminium alloy 2024-T3 was treated by two different methods of surface treatments i.e. by alkaline etching and warm water treatment followed by silanization method in order to enhance the adhesive bonding. Three different formulations of polyurethane adhesive by varying the NCO:OH ratios which were prepared from polyol polycaprolactone (PCL) based on palm kernel oil polyesteramide (PPKO) with a blend of aromatic and cycloaliphatic diisocyanate. Surface morphology, surface chemical analysis, wettability and surface roughness of the treated samples were characterised using field emission scanning electron microscopy and energy dispersive X-ray analysis (FESEM/EDX), X-Ray Photoelectron Spectroscopy (XPS), contact angle goniometry and surface profilometry, respectively. The influences of surface treatment techniques and conditions on durability of the joint strength and interfacial properties were explored by performing the single lap shear test and wedge test. The effects of NCO:OH ratios on PU adhesive strength were also investigated. Durability of PU adhesive bonding is found to display an interesting dependence on the surface treatments.

Durability of green polyurethane adhesive bonded aluminum alloy in dry and hydrothermal ageing conditions

ABSTRACTPolyurethane (PU) adhesives were prepared from the reaction of polycaprolactone (PCL) polyols based on palm kernel oil based polyesteramide (PPKO) with an aromatic and cycloaliphatic diisocyanate. Four different formulations of PU adhesives were prepared by varying the NCO : OH ratio, in order to investigate the effects of NCO : OH ratios on adhesion strength. The adhesive strength of metal–metal bonding both in dry and hydrothermal ageing—was determined by single lap shear joint testing. The resistance to hydrolysis of the PU adhesives was determined by performing water absorption tests. The water absorption test samples suggested that the durability of the adhesives correlated to lower water absorption due to higher NCO content. The correlation between the crosslinking of the PU network and adhesive strength was also studied by performing swelling tests. The higher NCO content showed that, the higher crosslink density of PUs led to higher cohesion and adhesion strengths. PU1.7 showed optimal properties in terms of durability and resistance to hydrolysis, whereas PU2.0 revealed deterioration in durability and resistance to hydrolysis due to the presence of greater micro‐voids content in the PU2.0 matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41151.

Influence of Isocyanate Structures on Mechanical Performance of Aluminum Bonded with Green Polyurethane Adhesive

Polyurethane (PU) adhesives were prepared from three different polyols based on polycaprolactone (PCL)/palm kernel oil (PKO) with an aromatic and cycloaliphatic diisocyanate. The adhesives were characterized through Fourier Transformer Infrared (FTIR) spectroscopy in order to ensure the formation of urethane and the completeness of polymer reaction. The effects of NCO/OH ratios and types of diisocyanate on PU adhesive strength were investigated. The adhesive strength of metal to metal bonding was determined by single lap shear joint testing. The correlation between crosslinking of PU network and adhesive strength was also studied by performing swelling tests.

Green Polyurethane Adhesive Bonding of Aluminum: Effect of Surface Treatments

Aluminum alloy 2024-T3 was treated by two different methods of surface treatments i.e. by alkaline etching and warm water treatment followed by silanization method in order to enhance the adhesive bonding. The effects of both the substrate surface condition and the adhesive properties on singlelap shear resistance were analysed. Three different formulation of polyurethane adhesive by varying the NCO:OH ratio which were prepared from polyol based on polycaprolactone (PCL)/palm kernel oil (PKO) with an aromatic and cycloaliphatic diisocyanate. Moreover, wettability tests were performed in order to evaluate the effect of all parameters mentioned above on the substrate/adhesive interaction. Surface treatment with warm water and ɣ-GPS gives better wettability and adhesive bonding compared to alkaline etching surface treatment.

Polyurethaneurea–silica nanocomposites: Preparation and investigation of the structure–property behavior

Nanocomposites consisting of thermoplastic polyurethane–urea (TPU) and silica nanoparticles of various size and filler loadings were prepared by solution blending and extensively characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), thermal analysis, tensile tests, and nanoindentation. TPU copolymer was based on a cycloaliphatic diisocyanate and poly(tetramethylene oxide) (PTMO-2000) soft segments and had urea hard segment content of 20% by weight. TPU/silica nanocomposites using silica particles of different size (29, 74 and 215 nm) and at different loadings (1, 5, 10, 20 and 40 wt. %) were prepared and characterized. Solution blending using isopropyl alcohol resulted in even distribution of silica nanoparticles in the polyurethane–urea matrix. FTIR spectroscopy indicated strong interactions between silica particles and polyether segments. Incorporation of silica nanoparticles of smaller size led to higher modulus and tensile strength of the nanocomposites, and elastomeric properties were retained. Increased filler content of up to about 20 wt. % resulted in materials with higher elastic moduli and tensile strength while the glass transition temperature remained the same. The fracture toughness increased relative to neat TPU regardless of the silica particle size. Improvements in tensile properties of the nanocomposites, particularly at intermediate silica loading levels and smaller particle size, are attributed to the interactions between the surface of silica nanoparticles and ether linkages of the polyether segments of the copolymers.

Linear glycidyl carbamate (GC) resins for highly flexible coatings

This invention relates to coating compositions comprising a linear glycidyl carbamate (GC) resin and a curing agent. The linear GC-resins were synthesized using linear and cycloaliphatic diisocyanates and a combination of diols and optional triols with glycidol. The combination of linear diisocyanates and diols introduces a more linear structure in the GC-resin compositions.

Fumed silica filled poly(dimethylsiloxane-urea) segmented copolymers: Preparation and properties

Novel fumed silica filled thermoplastic poly(dimethylsiloxane-urea) (TPSU) segmented copolymers were synthesized and characterized. TPSU copolymers were prepared from a cycloaliphatic diisocyanate, aminopropyl terminated PDMS oligomers with number average molecular weights of 3,200, 10,800 and 31,500 g/mol and 2-methyl-1,5-diaminopentane chain extender. Two different types of fumed silica HDK H2000 (hydrophobic) and HDK N20 (hydrophilic) were utilized and incorporated into silicone-urea copolymers in amounts of 1–60% by weight. Influence of the silica type (hydrophilic versus hydrophobic), amount of silica loading and the PDMS soft segment molecular weight on the morphology, tensile properties and modulus-temperature behavior of the nanocomposites were determined. Major observations of this study were: (i) under the blending conditions used, incorporation of silica does not seem to interfere significantly with the hydrogen bonding between urea groups, (ii) incorporation of silica does not affect the glass transition temperature of PDMS, (iii) incorporation of silica influences the tensile and thermomechanical properties of silicone-urea segmented copolymers significantly, (iv) average molecular weight of the PDMS soft segment in the silicone-urea copolymer plays a critical role on the improvement of the tensile properties of the fumed silica/TPSU composites.

Optimization of the structure of polyurethanes for bone tissue engineering applications

Polyurethanes containing 22–70 wt.% hard segments were developed and evaluated for bone tissue engineering applications. Aliphatic poly(ester-urethanes) were synthesised from poly(ε-caprolactone) diol with different molecular masses ( M = ∼530, 1250 and 2000 Da), cycloaliphatic diisocyanate 4,4′-methylenebis(cyclohexyl isocyanate) and ethylene glycol as a chain extender. Changes in macromolecule order with increasing hard segment content were observed via modulated differential scanning calorimetry. Depending on the hard segment content, a gradual variation in polyurethane surface properties was revealed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and static contact angle measurements. As the hard segments content increased the polyurethane surface exhibited more phase separation, a higher content of urethane moieties and higher hydrophilicity. The biocompatibility results indicated that proliferation of human bone-derived cells (HBDC) cultured in vitro improved with increasing hard segment content while the osteogenic potential of HBDC decreased with increasing hard segment content.

Contribution of soft segment entanglement on the tensile properties of silicone–urea copolymers with low hard segment contents

Abstract Novel, segmented thermoplastic silicone–urea (TPSU) copolymers based on rather high molecular weight aminopropyl terminated polydimethylsiloxane (PDMS) soft segments ( 10,800 and 31,500 g/mol), a cycloaliphatic diisocyanate (HMDI) and various diamine chain extenders were synthesized. Copolymers with very low urea hard segment contents of 1.43–14.4% by weight were prepared. In spite of very low hard segment contents, solution cast films showed very good microphase separation and displayed reasonable mechanical properties. Tensile strengths of TPSU copolymers showed a linear dependence on their urea hard segment contents, regardless of the structure of the diamine chain extender used. The modulus of silicone–urea copolymers is dependent on the urea concentration, but not on the extender type or PDMS molecular weight. When silicone–urea copolymers with identical urea hard segment contents were compared, copolymers based on PDMS-31,500 showed higher elongation at break values and ultimate tensile strengths than those based on PDMS-10,800. Since the critical entanglement molecular weight (Me) of PDMS is about 24,500 g/mol, these results suggest there is a significant contribution from soft segment chain entanglement effects in the PDMS-31,500 system regarding the tensile properties and failure mechanisms of the silicone–urea copolymers.

Microphase-separated structure and mechanical properties of norbornane diisocyanate-based polyurethanes

Norbornane diisocyanate (NBDI: 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane) is a new commercialized diisocyanate. NBDI-based polyurethane elastomers (PUEs) were prepared from poly(oxytetramethylene) glycol (PTMG), NBDI and 1,4-butanediol (BD) by a prepolymer method. Microphase-separated structure and mechanical properties of the NBDI-based PUEs were compared with general aliphatic and cycloaliphatic diisocyanate-based PUEs. The diisocyanates used were isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI). Regular polyurethanes were also prepared as hard segment models from each isocyanate and BD to understand the feature of each hard segment chain. The HDI-based PUE showed the largest Young's modulus and tensile strength in the four PUEs due to the ability of crystallization of the hard segment component and the strongest microphase separation. HMDI has both properties of aliphatic and cycloaliphatic diisocyanates because of its high symmetrical chemical structure compared with NBDI and IPDI. On the other hand, the NBDI- and IPDI-based PUEs have an inclination to phase mixing, leading to decreased Young's modulus and tensile strength. The NBDI-based PUE exhibited better thermal properties at high temperatures due to stiff structure of NBDI.

Polyurethane anionomers synthesised with aromatic, aliphatic or cycloaliphatic diisocyanates, polyoxyethylene glycol and 2,2-bis-(hydroxymethyl)propionic acid. Part 3. Electrical properties of polyurethane coatings

The following electrical properties were found for polymer coatings obtained from polyurethane anionomers synthesised with the use of various diisocyanates: volume resistivity, permittivity and dielectric dissipation factor. The effects were discussed from the molecular structures and phase structures of those anionomers on the value of their ionic conductivity and polarizability. The anionomer prepared from the aliphatic diisocyanate was found to offer ionic conductivity; hence, that material can be considered to be a solid electrolyte, which exhibits a considerable susceptibility to structural modifications in the alternating electric field.

Polyurethane anionomers synthesised with aromatic, aliphatic or cycloaliphatic diisocyanates, polyoxyethylene glycol and 2,2-bis-(hydroxymethyl)propionic acid. Part II. Supermolecular structure. Thermal properties

Small angle X-ray scattering and differential scanning calorimetry methods were employed to characterise the internal order of structural phases present in polyurethane coatings obtained as a result of water evaporation from anionomer dispersions. Those anionomers were produced in the reaction of aromatic, cycloaliphatic and aliphatic diisocyanates with polyoxyethylene glycol, 2,2-bis-(hydroxymethyl)propionic acid and 1,6-hexamethylenediamine. The decisive effects were found from ionic and polar structures within the rigid urethane and urea segments on the ordered arrangement degree of the supermolecular structures in the obtained anionomers. That becomes apparent in differential scanning calorimetry thermograms and contributes to improved thermal stability of the produced polyurethane coatings.

Influence of Catalyst Type on Biocompatibility of Polyurethanes

Segmented polyurethanes (PUR) based on poly(ε-caprolactone)diol (PCL) as soft segments and cycloaliphatic diisocyanate were obtained. Two different types of catalysts were used for synthesis: dibutyltin dilaurate (DBTDL) and iron (III) acetylacetonate Fe(acac)3. Structure, thermal analysis, water absorption of obtained polyurethanes were studied. Polyurethanes catalyzed by Fe(acac)3 have lower glass transition temperature (Tg2) and melting temperature (Tm2) of hard domains in comparison with polyurethanes synthesized with DBTDL. Amount of absorbed water is in the range of 1,0-2,0% and is higher for PUR catalyzed by DBTDL. SEM observations show that type of catalyst used in synthesis affect structure of polyurethanes. Biological test XTT was done in order to determine influence of various metallic compounds used as catalyst on viability of human bone cell culture. The XTT results indicate no influence on viability of human osteoblasts cultured on the obtained PUR.