Diisocyanate Structure Research Articles

Cross-Linked Fluorinated Polyurethanes against Chemical Warfare Agent Simulants: Properties Affected by the Structure of Diisocyanate

Cross-Linked Fluorinated Polyurethanes against Chemical Warfare Agent Simulants: Properties Affected by the Structure of Diisocyanate

Synthesis of Polyurethane from Apricot Kernel Oil and Characterization

In the study, natural origin polyol was obtained from apricot kernel oil. The obtained polyol was used in the synthesis of polyurethane, which is an industrially important polymer. Obtaining polyol from apricot kernel oil was firstly epoxidized with a two-step process and then converted to the desired polyol structure by oxirane ring opening. The obtained biocompatible polyol structure was subjected to polymerization process with the hexamethylene diisocyanate structure. The obtained polyurethane structures were characterized chemically, thermally and morphologically. The chemical structure was investigated by FTIR spectra. The thermal stability, Tg values and decomposition temperatures of the obtained polyurethane structure were investigated by TGA, DTA and DSC techniques. The basic morphological features of the polyurethane structure were evaluated by SEM analysis.

Synthesis and properties of water‐dispersible polyurethanes based on various diisocyanates and PEG as the hard segment

AbstractWater‐dispersible polyurethanes are a greener alternative to polyurethane solutions in organic solvents. Various polyurethane materials were prepared by a two‐step polymerization procedure of polypropylene glycol with Mn of 2000, polyethylene glycol with Mn of 1500, and diisocyanates with different chemical structures, aliphatic, cycloaliphatic and aromatic. It was investigated how the diisocyanate structure affected the molecular morphology, contact angle measurements, and physical characteristics of water‐dispersible polyurethanes. FTIR and NMR measurements showed a close relationship between the intermolecular connections and the hard segment structure, mainly of the diisocyanate used. Also, the polarized light method showed that the presence of the PEG in the hard domain improved aggregation through physical interactions due to its structural flexibility and mobility. These water‐dispersible polyurethanes can assure the use of these polyurethane materials in a broad range of applications with increased environmental protection.

The Influence of Diisocyanate Structure on Thermal Stability of Thermoplastic Polyurethane Elastomers Based on Diphenylmethane-Derivative Chain Extender with Sulfur Atoms.

The work is a continuation of the research on thermoplastic polyurethane (TPU) elastomers containing sulfur atoms which are incorporated into the polyurethane chain using aliphatic-aromatic chain extenders. These materials show some improved properties in relation to conventional ones, e.g., adhesion to metals, bacterial resistance and refractive index. The present study deals with the detailed characteristics of the process of thermal decomposition of TPU elastomers obtained from 2,2'-[methylenebis(1,4-phenylenemethylenethio)]diethanol, 1,1'-methanediylbis(4-isocyanatobenzene) (MDI) or 1,6-diisocyanatohexane (HDI) and poly(oxytetramethylene) diol of Mn = 2000 g/mol by thermogravimetric analysis coupled on-line with Fourier transform infrared spectroscopy. The analysis was performed under inert and oxidative conditions. All TPU elastomers were found to have a relatively good thermal stability, with those based on aromatic diisocyanate being at an advantage. In helium, they are stable up to 280-282 °C (from HDI) and 299-301 °C (from MDI), whereas in synthetic air up to 252-265 °C (from HDI) and 261-272 °C (from MDI), as measured by the temperature of 1% mass loss. Depending on the content of the hard segments and the tested atmosphere, the TPU elastomers decompose from one to four stages. From the analysis of the volatile decomposition products, it follows that the decomposition of both types of hard segments was accompanied by the evolution of carbonyl sulfide, carbon dioxide, water, sulfide dioxide, alcohols and aromatic compounds. For the hard segment derived from HDI, isocyanates, amines, and unsaturated compounds were also identified, while for the MDI-derived one, aldehydes were discovered. In turn, the polyether soft segment decomposed mainly into aliphatic ethers, aldehydes, and carbon monoxide.

The Role of Diisocyanate Structure to Modify Properties of Segmented Polyurethanes

Segmented thermoplastic polyurethanes (PU) were synthetized using a polycarbonatediol macrodiol as a flexible or soft segment with a molar mass of 2000 g/mol, and different diisocyanate molecules and 1,4-butanediol as a rigid or hard segment. The diisocyanate molecules employed are 3,3'-Dimethyl-4,4'-biphenyl diisocyanate (TODI), 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-Methylenebis(phenyl isocyanate) 1-isocyanato-4-[(4-phenylisocyanate)methyl]benzene and 1-isocyanate-4-[(2-phenylisocyanate) methyl]benzene (ratio 1:1) (MDIi), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI). The polyurethanes obtained reveal a wide variation of microphase separation degree that is correlated with mechanical properties. Different techniques, such as DSC, DMA, and FTIR, have been used to determine flexible-rigid segment phase behavior. Mechanical properties, such as tensile properties, Shore D hardness, and "compression set", have been determined. This work reveals that the structure of the hard segment is crucial to determine the degree of phase miscibility which affects the resulting mechanical properties, such as tensile properties, hardness, and "compression set".

Synthesis and Structure of 2-Hydroxypropyl Methacrylate-Capped Isophorone Diisocyanate and Poly(Propylene Glycol) Urethane Mixtures and the Properties of their UV-Cured Co-Networks with Isobornyl Methacrylate

Polyurethane acrylate prepolymers with different contents of HIPIH and HIH were synthesized via reacting excessive isophorone diisocyanate (IPDI) with poly(propylene glycol) (PPG) and then end-capping with 2-hydroxypropyl methacrylate (HPMA) in isobornyl methacrylate (IBOMA). After the addition of the photoinitiator PI 1173, the resulting prepolymer resins were irradiated by UV light to form cured materials. The structures of the prepolymers were confirmed by 1H NMR, FT-IR, and GPC. SEM analyses proved that no obvious phase separation was observed within the cured sample. As the content of HIH increased, the viscosity of the prepolymers increased slightly. In addition, the gel content, solvent resistance, Shore hardness, Young's modulus, and the tensile strength of the cured films increased, whereas the elongation at break decreased gradually. The volume shrinkage of the cured samples ranged between 4.5% and 4.8%. DMA analyses showed that the Tgs of the cured samples increased as more HIH structures existed. TGA analyses revealed that the cured samples had high thermal stability. This solvent-free fabrication process was simple, convenient, and controllable. By simply regulating the contents of HIPIH and HIH in the prepolymers, the performances of the cured materials could be adjusted to a wide range.

Single-Ion Conducting Polymer Electrolytes Based on Random Polyurethane–Urea with Different Diisocyanate Structures for Lithium Batteries

Polyurethane–urea ionomers based on poly(ethylene oxide) (PEO) with various hard segment contents were synthesized from diisocyanates with different symmetries and planarities. The influence of the random copolymer microphase structure (including the phase separation morphology and hydrogen bonding behavior) on the ion states and ion migration was investigated. The soft phase could maintain a low glass transition temperature to yield samples with good ionic conductivity when the hard segment was less than 48 wt %. Furthermore, the hard phase and hydrogen bonds could provide good mechanical strength. Fourier transform infrared spectroscopy and small-angle X-ray scattering confirmed that ionomers with a smaller degree of phase separation had a high fraction of ions in isolated ion pairs. Coupled with faster segmental dynamics and ion mobility from the depressed Tg, the polyurethane–urea ionomer simultaneously showed high strength and ionic conductivity. After plasticization, the prepared single-ion conductor was successfully tested in lithium cells, demonstrating outstanding discharge capacity (166 mAh g–1), Coulombic efficiency (96.5%), and retention (92.6% after 100 cycles) at 0.1 C and high temperature.

Effect of diisocyanate structure on steric restructuring of hindered urea bonds for self-healable coating

Hindered-urea bonds (HUBs), made of bulky amine and isocyanate, are reversible and the reversibility generally comes from the steric hindrance of the bulky substituents on the amine. In this study, the steric effects of diisocyantes (DIs) on the reversibility of HUBs and HUB-bearing polymers were studied. An acrylic prepolymer bearing tertiary-butyl amine (PtB) was prepared and crosslinked with five different DIs. The reversibility of the HUBs as well as the thermodynamic and self-healing behaviours of the HUB-bearing polymer networks (PtB-DIs) were investigated with respect to the structure of alkyl substituents on DIs. Proton nuclear magnetic resonance (1H NMR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and oscillatory rheometry were performed, and it was confirmed that the reversibility of the HUB increases as the order of isocyanate group increases (1° > 2° > 3°). Self-healing behaviours were examined by single scratch tests, and the self-healing efficiency increased in the same order. Blending of two isocyanates, 1,4-bis(isocyanatomethyl)benzene (XDI) and tetramethylxylene diisocyanate (TMXDI), expanded the choices for the mechanical and self-healing properties of the polymers. It was remarkable that the mechanical properties of the HUB-bearing polymers at ambient temperature were more significantly affected by the spacer structure of diisocyanate than the steric hindrance.

Preparation, Structure and Properties of Urethane-Containing Elastomers Based on Epoxy Terminal Oligomers.

The effect of polyester oligoethylene adipate molecular weight, diisocyanate structure, and chain extender on the properties of epoxyurethane-based oligomer elastomers was studied in this research. Oligoethylene adipates were obtained via polycondensation of adipic acid and ethylene glycol. Epoxyurethane oligomers were synthesized according to a two-step route with an oligodiisocyanate as an intermediate product. The elastomers with hard urethane hydroxyl blocks were synthesized from oligodiisocyanates. The deformation and strength properties of the elastomers were studied.

Influence of the chemical structure of diisocyanate on the electrical and thermal properties of in situ polymerized polyurethane-graphene composite films.

If the conductivity and thermal properties of polyurethane films are improved with fillers, they can be used in wearable electronics, strain sensors, etc. In this regard, the present study aims to examine the effects of various diisocyanates as hard segments on polyurethane-graphene (PU/G) nanocomposites. To achieve this, nanocomposites are synthesized, first, and then the structural, electrical, and thermal properties of them are investigated. The results indicate that only PU/G composites based on toluene diisocyanate (TDI), methylene dicyclohexyl diisocyanate (HMDI), and hexamethylene diisocyanate (HDI) have non-zero I-V curves and are in the percolation zone. The thermal stability of the PU/G composite based on cyclo-aliphatic isophorone diisocyanate (IPDI) is higher than that of the others, while TDI-PU/G has the lowest thermal stability due to its chemical structure. The results show that HDI-PU/G, based on less dangerous diisocyanate, is a more flexible nanocomposite. It also has electrical advantages, a wider range of working temperatures, and good thermal stability. Furthermore, the maximal Seebeck coefficient and voltage belong to it, which are around 2.5 mV °C-1 at 45 °C and 0.15 V at 85 °C, respectively.

Role of Diisocyanate Structure on Self‐Healing and Anticorrosion Properties of Waterborne Polyurethane Coatings

AbstractOrganic coatings are extensively investigated as possible solution to prevent or at least retard the occurring of corrosion processes on metal surfaces. Their actual breakthrough is still hampered by the risk of barrier properties loss because of local failure of the coating integrity. To address this issue, self‐healing coatings, which are intrinsically able to recover from damages upon exposure to external stimuli, are currently gaining increasing attention. Herein, waterborne polyurethanes (PU) are synthesized, and a Diels–Alder adduct is added into the polymeric backbone to endow the material with self‐healing functionality. The effect of different diisocyanate in PU synthesis is explored, namely isophorone diisocyanate, 4,4′‐dicyclohexylmethane diisocyanate (HMDI), and hexamethylene diisocyanate. The obtained results highlight the key role of the interactions among soft and hard segments in ultimately defining the coating performances. Actually, the combination of Fourier transform infrared spectroscopy, atomic force microscopy and X‐ray diffration analysis reveals that the HMDI‐based PU have showed the best balance in terms of H‐bonding strength among hard segments and crystallinity degree in the soft ones. This allows to reach a good compromise in terms of mechanical resistance, anticorrosion properties, and self‐healing ability.

Influence of Hard Segment Content and Diisocyanate Structure on the Transparency and Mechanical Properties of Poly(dimethylsiloxane)-Based Urea Elastomers for Biomedical Applications.

The effect of hard segment content and diisocyanate structure on the transparency and mechanical properties of soft poly(dimethylsiloxane) (PDMS)-based urea elastomers (PSUs) was investigated. A series of PSU elastomers were synthesized from an aminopropyl-terminated PDMS (: 16,300 g·mol−1), which was prepared by ring chain equilibration of the monomers octamethylcyclotetrasiloxane (D4) and 1,3-bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS). The hard segments (HSs) comprised diisocyanates of different symmetry, i.e., 4,4′-methylenebis(cyclohexyl isocyanate) (H12MDI), 4,4′-methylenebis(phenyl isocyanate) (MDI), isophorone diisocyanate (IPDI), and trans-1,4-cyclohexane diisocyanate (CHDI). The HS contents of the PSU elastomers based on H12MDI and IPDI were systematically varied between 5% and 20% by increasing the ratio of the diisocyanate and the chain extender APTMDS. PSU copolymers of very low urea HS contents (1.0–1.6%) were prepared without the chain extender. All PSU elastomers and copolymers exhibited good elastomeric properties and displayed elongation at break values between 600% and 1100%. The PSUs with HS contents below 10% were transparent and became increasingly translucent at HS contents of 15% and higher. The Young’s modulus (YM) and ultimate tensile strength values of the elastomers increased linearly with increasing HS content. The YM values differed significantly among the PSU copolymers depending on the symmetry of the diisocyanate. The softest elastomer was that based on the asymmetric IPDI. The elastomers synthesized from H12MDI and MDI both exhibited an intermediate YM, while the stiffest elastomer, i.e., that comprising the symmetric CHDI, had a YM three-times higher than that prepared with IPDI. The PSUs were subjected to load–unload cycles at 100% and 300% strain to study the influence of HS morphology on 10-cycle hysteresis behavior. At 100% strain, the first-cycle hysteresis values of the IPDI- and H12MDI-based elastomers first decreased to a minimum of approximately 9–10% at an HS content of 10% and increased again to 22–28% at an HS content of 20%. A similar, though less pronounced, trend was observed at 300% strain. First-cycle hysteresis among the PSU copolymers at 100% strain was lowest in the case of CHDI and highest in the IPDI-based elastomer. However, this effect was reversed at 300% strain, with CHDI displaying the highest hysteresis in the first cycle. In vitro cytotoxicity tests performed using HaCaT cells did not show any adverse effects, revealing their potential suitability for biomedical applications.

Sustainable Shape-Memory Polyurethane from Abietic Acid: Superior Mechanical Properties and Shape Recovery with Tunable Transition Temperatures.

A new chemical architecture from abietic acid, consisting of a cycloaliphatic unsaturated terminal diisocyanate (AADI) structure, is synthesized and fully characterized. The AADI is then used to construct an amorphous and biocompatible shape-memory polyurethane (SMPU) network system with adjustable cross-linking densities over a wide range. The SMPU network exhibits good shape-memory properties with a shape fixing rate of greater than 98 % and a shape recovery rate of 95 %. In vitro hydrolytic biodegradation weight loss ratio of SMPUs reaches 71 % within eight weeks. The physical properties of these SMPUs are comparable to those reported for SMPUs obtained from commercially available petroleum-derived diisocyanates. This is the first time that multiple SMPU networks based on abietic acid have been reported. These environmentally-friendly SMPUs display a wide range of physicomechanical properties with promising hydrolytic degradability, showing good potential for practical application.

Study on the surface properties and thermal stability of polysiloxane-based polyurethane elastomers with aliphatic and aromatic diisocyanate structures

A series of polysiloxane-based polyurethane elastomers with aliphatic and aromatic diisocyanate structures are prepared using a two-step polymerization method. First, tolylene diisocyanate (TDI); dicyclohexylmethane 4,4′-diisocyanate (H12MDI); and hexamethylene diisocyanate (HDI) separately react with polycarbonate diol (PCDL) to produce polyurethane prepolymer, and furthermore, polysiloxane (PDMS) is added to the system to produce different polymers. The effect of different diisocyanate structures on mechanical properties, thermal stability, surface topography, and hydrophobic properties are explored. The results show that when the mass loss is higher than 50% during thermal decomposition, TDIPU exhibits relatively excellent thermal stability, which may be caused by the exposure of the silicone inside the polymer. HDIPU shows high hydrophobicity and low surface free energy, which is mainly related to a large amount of Si enriched on the surface. These differences are mainly caused by different molecular structures.

Synthesis and molecular interaction of tung oil‐based anionic waterborne polyurethane dispersion

AbstractIn the present work, four types of anionic waterborne polyurethane dispersions (APUD) based on polytetramethylene ether glycol (PTMG) and two aliphatic diisocyanates, dicyclohexylmethane diisocyanate (HMDI) or isophorone diisocyanate (IPDI), were prepared by polymerization methods which for the first time controlled the location (soft or hard segment) of hydroxylated tung oil (HTO) incorporation into the final APUD. The resulting HTO‐containing APUD polymers (HTO‐APUDs) with postpolymerization crosslinking capability were characterized using FTIR, DMA, AFM and water imbibition methods, and compared to model compounds synthesized to have the same parts of chemical structural linkages for band assignment. A common PUD sample, as well as polypropylene oxide (PPG) with molecular weight similar to HTO (Mn = 400), was used to replace it for preparing control samples to highlight the role of long branched chains and conjugated double bonds in HTO. Based on the analysis of multiple H‐bond interactions, the relationship of HTO location in the APUD polymer structure to the soft/hard segment compatibility and the diisocyanate structure was further studied. This work is expected to provide basic data for properties regulation in practical applications by adjusting the chain and phase structure, as well as the intermolecular interactions, in these APUDs.

Effects of Diisocyanate Structure and Disulfide Chain Extender on Hard Segmental Packing and Self-Healing Property of Polyurea Elastomers.

Four linear polyurea elastomers synthesized from two different diisocyanates, two different chain extenders and a common aliphatic amine-terminated polyether were used as models to investigate the effects of both diisocyanate structure and aromatic disulfide chain extender on hard segmental packing and self-healing ability. Both direct investigation on hard segments and indirect investigation on chain mobility and soft segmental dynamics were carried out to compare the levels of hard segmental packing, leading to agreed conclusions that correlated well with the self-healing abilities of the polyureas. Both diisocyanate structure and disulfide bonds had significant effects on hard segmental packing and self-healing property. Diisocyanate structure had more pronounced effect than disulfide bonds. Bulky alicyclic isophorone diisocyanate (IPDI) resulted in looser hard segmental packing than linear aliphatic hexamethylene diisocyanate (HDI), whereas a disulfide chain extender also promoted self-healing ability through loosening of hard segmental packing compared to its C-C counterpart. The polyurea synthesized from IPDI and the disulfide chain extender exhibited the best self-healing ability among the four polyureas because it had the highest chain mobility ascribed to the loosest hard segmental packing. Therefore, a combination of bulky alicyclic diisocyanate and disulfide chain extender is recommended for the design of self-healing polyurea elastomers.

Development of high refractive and high water content polythiourethane/AA hydrogels for potential artificial cornea implants

Two novel thiol-terminated monomers, ethylene glycol bis(mercaptoacetate) (EGBMA) and glycerol tri(mercaptoacetate) (GTMA), were prepared via esterification reaction of mercaptoacetic acid with ethylene glycol or glycerol. Then the synthesized thiol-terminated monomers were reacted with excess diisocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate (TDI) or methylenediphenyl diisocyanate (MDI), followed by reacting with 2-hydroxyethyl methacrylate (HEMA) to get several different polymerizable polythiourethane (PTU) precursors. Subsequently, a series of high refractive index (RI) and high water content polythiourethane/acrylic acid (PTU/AA) hydrogels was successfully synthesized from the polythiourethane precursors via a simple ultraviolet-light-initiated free radical co-polymerization method. The resulting hydrogels are clear and transparent, and their RIs were measured to be as high as 1.514–1.548 and 1.396–1.441 in dry and hydrated state, respectively, and water content of the hydrogels can be reached 62.9–86.2%, which can be tuned by varying the structure of diisocyanate and polythiourethane, or the weight ratio of PTU to PAA. In vitro cytotoxicity assays suggested all the hydrogels exhibited low cytotoxicity towards human corneal epithelial cells (HCECs). Hence, the high RI and high water content hydrogels developed in this work might potentially be an excellent candidate for artificial corneal implants.

Microphase separation and mechanical properties of the polyurethanes based on the high soft segment poly(bis‐azidomethyl oxetane)/tetrahydrofuran binder

The correlation of diisocyanate structure with hydrogen bonding and microphase separation and further their influence on mechanical property was investigated in high soft segment (about 90 wt%) energetic poly(bis‐azidomethyl oxetane/tetrahydrofuran) polyurethane binder. The hydrogen bonding analysis from Fourier transform infrared spectroscopy demonstrated that the limited intersegmental hydrogen bonding can occur in the hard domain, and small‐angle X‐ray scattering results also showed that the absence of high‐order peaks in synthesized high soft segment polyurethanes. However, coplanar and symmetric diisocyanate and its inner benzene ring are favorable to ordered arrangement of hard segment, and further mircophase seperation enhance the tensile strength. POLYM. ENG. SCI., 59:724–729, 2019. © 2018 Society of Plastics Engineers

Thermal degradation behavior and X-ray diffraction studies of chitosan based polyurethane bio-nanocomposites using different diisocyanates

Five different samples of chitosan based polyurethane bio-nanocomposites (PUBNCs) were synthesized by step growth polymerization technique. Five different diisocyanates were used by keeping hydroxyl terminated polybutadiene (HTPB)/1,4-butane diol (1,4-BDO)/chitosan (CS) and montmorillonite (MMT) clay ratios constant (PUR1–PUR5). For comparative studies, PUR-6 was prepared without CS and clay components. Molecular characterizations of polyurethane (PU) films were carried out by FTIR and NMR which was found to have confirmatory evidence of the proposed structures. X-ray diffraction angles (2θ), d-spacing and intensities of chitosan based samples (PUR1-PUR5) and PUR-6 indicated that crystalline behavior of PUBNCs is influenced by varying diisocyanate structures. TGA/DTA results revealed that chitosan increased thermal stability of PU samples; it also enhanced the mechanical strength and decreased the glass transition temperature (Tg) of all the samples. Based on the above mentioned facts this study suggests the best usage of PUs according to the operational and environmental conditions.

Vanillin derived a carbonate dialdehyde and a carbonate diol: novel platform monomers for sustainable polymers synthesis.

Vanillin has been regarded as one of the important biomass-based platform chemicals for aromatic polymers synthesis. Herein, novel symmetric bis(4-formyl-2-methoxyphenyl)carbonate (BFMC) and bis(4-(hydroxymethyl)-2-methoxyphenyl)carbonate (BHMC) polymeric monomers have been synthesized in high yields using vanillin as a raw chemical, which have been submitted for polymer synthesis via well-established polymeric strategies. A new class of poly(carbonate ester)s oligomers with amide moieties in their side chain can be prepared by using the BFMC as one of monomers via the Passerini three compound reaction (3CR). A new class of poly(carbonate ester)s oligomers and poly(carbonate urethane)s can be prepared via reactions between BHMC with dicarboxylic acid chlorides and diisocyanates, respectively. Their structure have been confirmed by 1H NMR, 13C NMR and FTIR, and the gel permeation chromatograph (GPC) analysis shows that the Mn of poly(carbonate ester)s oligomers ranges from 3100 to 7900 with PDI between 1.31 and 1.65, and the Mn of poly(carbonate urethane)s ranges from 16 400 to 24 400 with PDI ranging from 1.36 to 2.17. The DSC analysis shows that the poly(carbonate ester)s oligomers have relative low Tg ranging from 37.4 to 74.1 °C, and the poly(carbonate urethane)s have Tg ranging from 97.3 to 138.3 °C, mainly correlating to the structure of dicarboxylic acid chlorides and diisocyanates used.