Physical properties and morphology of crosslinked polyurethane synthesized from para‐phenylene diisocyanate and polyether polyol

A series of crosslinked polyurethanes (PUs) were synthesized from para‐phenylene diisocyanate, 2‐(hydroxymethyl)‐2‐ethyl propane‐1,3‐diol (TMP), and butane‐1,4‐diol as the hard segments and poly(oxytetramethylene glycol) as the soft segments. The effects of TMP on the physical properties and microphase structure of the PUs were studied with dynamic mechanical analysis, Fourier transform infrared–attenuated total reflection spectroscopy, small‐angle X‐ray scattering (SAXS), and mechanical testing. We found that the storage modulus, hydrogen bonding with carbonyl groups, SAXS intensity, and hysteresis values decreased with increasing TMP; this indicated that the degree of microphase separation decreased with the increasing crosslinking density introduced by TMP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45241.     

Synthesis and characterization of polyurethane urea based on fluorine‐containing bisphenoxydiamine

A fluorine‐containing bisphenoxydiamine, 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane (BAPF₆P), was synthesized and characterized by means of Fourier transform infrared spectrometry (FTIR), NMR, and elemental analysis. The obtained BAPF₆P was used as a chain extender to prepare polyurethane urea (PUU), whose morphology and properties were measured through FTIR, differential scanning calorimetry, thermogravimetric analysis, tensile measurements, and atomic force microscopy. The results show that the PUU elastomers based on BAPF₆P exhibited good mechanical properties and thermal stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1863–1869, 2006     

Synthesis and characterization of interpenetrating polymer networks from polyurethane and poly(ethylene glycol) diacrylate

Interpenetrating polymer networks (IPNs) combining polyurethane (PU) and poly(ethylene glycol) diacrylate (PEGDA) networks were prepared with simultaneous polymerization. PU was synthesized from biocompatible and biodegradable poly(ε-caprolactone) diol, and the hydroxyl group of poly(ethylene glycol) was substituted with a crosslinkable acrylate group. The effects of the PU/PEGDA compositions and the crosslink density of PU and PEGDA on the thermal properties, swelling ratio, surface energy, mechanical properties, and morphologies were investigated. The mechanical properties of PEGDA networks were improved by the presence of PU networks, particularly in the 75% PU/25% PEGDA IPNs. All PU/PEGDA IPNs showed a microphase-separated structure with cocontinuous morphology, as observed by atomic force microscopy, which was in agreement with the results of swelling ratio and dynamic mechanical thermal analysis measurements. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Flexible polyurethane foams modified with biobased polyols: Synthesis and physical‐chemical characterization

A series of flexible polyurethane foams with different polyol compositions were synthesized through the replacement of a portion of the petroleum‐based polyether polyol with biobased polyols, namely, glycerol (GLY) and hydroxylated methyl esters (HMETO). HMETO was synthesized by the alkaline transesterification of tung oil (TO; obtaining GLY as a byproduct) and the subsequent hydroxylation of the obtained methyl esters with performic acid generated in situ. FTIR spectroscopy, ¹H‐NMR, and different analytical procedures indicated that the hydroxyl content increased significantly and the molecular weight decreased with respect to those of the TO after the two reaction steps. The characterization of the obtained foams, achieved through the measurement of the characteristic reaction times, thermal and dynamic mechanical analysis, scanning electronic microscopy, and density measurements, is reported and discussed. The most important changes in the modified foams were found with the addition of GLY to the formulation; this led to an increased foam density and storage rubbery modulus, which were associated with a higher crosslinking density because of the decrease in the chain length between crosslinking points. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43831.     

Polyester polyols and polyurethanes from ricinoleic acid

Triols of molecular weights (MWs) 1000–4000, suitable for flexible foams, were prepared by transesterification of methyl esters of ricinoleic acid with trimethylol propane. These polyols were noncrystallizing, relatively low‐viscosity liquids. They were reacted with diphenylmethane diisocyanate (MDI) to obtain elastomers having glass transition temperatures below ?60°C. Polymer networks from high‐MW polyols exhibited relatively high sol fractions suggesting that some cyclization occurred during polyol preparation. The low Shore hardness, relatively low strength and modest elongation of the elastomers were attributed to the specific structure of polyricinoleic chains and the presence of dangling chains, serving as plasticizers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Click‐ligation of coumarin to polyether polyols for polyurethane foams

A simple strategy for the synthesis and functionalization of polyurethanes is described. Anionic ring‐opening polymerization was combined with ‘click’ chemistry to synthesize polyols with fluorescent properties. This route allows the incorporation of a wide range of functionalities in the polyols with an easy, clean and highly selective process compatible with several types of functional groups. The proposed strategy opens the way to the production, in a cost‐effective way, of ‘smart’ polyurethanes with non‐conventional properties like fire retardancy, antimite properties, antibacterial properties, etc. Alkynyl groups were introduced into the polyol chains by the controlled addition of glycidyl propargyl ether as co‐monomer during a conventional anionic ring‐opening copolymerization with propylene oxide. Subsequently 4‐azidomethyl‐7‐methoxycoumarin molecules were introduced onto the alkynyl‐polyether polyols by copper‐catalysed cycloaddition reactions to produce end‐functionalized polyols. The chemical structure of the novel polyols was characterized using infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography with triple detection and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy. These characterization techniques confirmed the presence of a considerable amount of functional groups in the structure of the polyols. Finally, various fluorescent rigid foams, based on the functionalized polyols, were synthesized. Copyright © 2012 Society of Chemical Industry     

Vinyl ether‐based polyacetal polyols with various main‐chain structures and polyurethane elastomers prepared therefrom: Synthesis,structure, and functional properties

Novel acid degradable polyacetal polyols and polyacetal polyurethanes able to controlled acid degradation were developed. Polyacetal polyols with various main‐chain structures were synthesized by polyaddition of various vinyl ethers with a hydroxyl group [4‐hydroxy butyl vinyl ether (CH₂?CH? O? CH₂CH₂CH₂CH₂? OH), 2‐hydroxy ethyl vinyl ether (CH₂?CH? O? CH₂CH₂? OH), diethylene glycol monovinyl ether (CH₂?CH? O? CH₂CH₂OCH₂CH₂? OH), and cyclohexanedimethanol monovinyl ether (CH₂?CH? O? CH₂? C₆H₁₀? CH₂? OH)] with p‐toluenesulfonic acid monohydrate (TSAM) as a catalyst in the presence of the corresponding diols [1,4‐butandiol (HO? CH₂CH₂CH₂CH₂? OH), ethylene glycol (HO? CH₂CH₂? OH), diethylene glycol (HO? CH₂CH₂OCH₂CH₂? OH), and 1,4‐cyclohexanedimethanol (HO? CH₂? C₆H₁₀? CH₂? OH)], respectively. Polyacetal polyurethanes were prepared by a two‐step polymerization, using the synthesized polyacetal polyols, 4,4′‐diphenylmethane diisocyanate (MDI), and 1,4‐butandiol (BD) as a chain extender. Depending on the main‐chain structures, these polyurethanes had different glass transition temperature (from ?44 to 19 °C) and properties such as hydrophobic or hydrophilic. Polyurethanes containing the hydrophilic main‐chain exhibited the thermoresponsiveness and had the certain volume phase transition temperature (VPTT). The polyacetal polyurethanes were flexible elastomers around room temperature (～25 °C) and thermally stable (T_d ≥ 310 °C) and additionally exhibited smooth degradation with a treatment of aqueous acid in THF at room temperature to give the corresponding raw material diols. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44088.     

Synthesis and characterization of novel laccol based polyurethanes

Development of polyurethanes (PU) has come a long way from their origin in 1937 and has unique applications in a diverse set of fields. Recent PU developments are focusing more on the naturally-derived diols in the synthesis process in an effort to make them more environmentally friendly. In this study, three different diisocyanates (aliphatic, cycloaliphatic, and aromatic diisocyanates) were combined with laccol, which extracted from Vietnamese lacquer sap (Toxicodendron succedanea) to synthesize novel PUs. Influence of the different diisocyanates in novel PUs, hydrogen bonding capability, and crosslinking ability were investigated to provide a broader characteristic scope for future developments. Resulting materials illustrated good thermal stability after exposed to higher temperatures and the hydrogen bonding regions corresponding to N H (3326 cm⁻¹) and CO (1652 cm⁻¹) groups were shifted to higher wavenumber according to Fourier transform infra-red spectroscopy analysis. Further curing occurred with temperature treatment and improved the overall quality of novel PUs. Powder X-ray analysis, micro hardness, and swelling analysis were utilized to identify molecular packing and crosslinking effects. Higher crosslink density observed for cycloaliphatic and aromatic diisocyanate incorporated novel polyurethanes compared to aliphatic diisocyanate incorporated polyurethane.     

Synthesis and characterization of polyurethane rigid foams from polyether polyols with isosorbide as the bio-based starting agent

In this study, with the isosorbide as bio-based starting agent, a series of bio-based polyether polyols with different hydroxyl values were synthesized and used to prepare polyurethane rigid foams (PURF). The structures of as-synthesized polyols were studied by FT-IR and ¹H NMR methods. The thermal properties, mechanical properties, microscopic morphology, thermal conductivity and dimensional stability of PURF have been characterized by several physico-chemical and ASTM methods. The initial decomposition temperature T_5% and the maximum decomposition temperature T_max for PURF from isosorbide-based polyols with 458 mg KOH/g hydroxyl value are about 312 °C and 354 °C, improved 61 °C and 75 °C comparing with the PURF from 1,2-propanediol-based polyols. The maximum compressive strength of PURF from isosorbide-based polyols is 141 kPa, comparing with 118 kPa of PURF from 1,2-propanediol-based polyols. Meanwhile, the dimensional stability of PURF from isosorbide-based polyols has been improved twofold, and the water absorption was obviously reduced by 50%. All these results suggest that polyols of isosorbide-based starting agent should be promising feedstock for PURF with high performance.     

Synthesis and characterization of rubber‐seed‐oil‐based polyurethanes

Novel biobased polyurethanes were synthesized from rubber seed oil (RSO), a renewable resource. The RSO monoglyceride, together with xylene and hexamethylene diisocyanate (HMDI), was employed to synthesize the desired urethane‐based prepolymer with isocyanate (NCO)‐terminated end groups followed by curing. The degrees of crosslinking of the polyurethane after curing were assessed with their swelling behavior. The properties of the resulting polyurethanes were found to be dependent on the type of diisocyanate and their molar ratios to the RSO monoglyceride. The network structures, which were assessed through swelling studies, showed that networks based on HMDI with an NCO/OH ratio of 1.50 were better crosslinked than with those toluene diisocyanate. The thermal properties of the samples analyzed by thermogravimetric analysis showed two and three decomposition stages in aliphatic‐ and aromatic‐based RSO polyurethanes, respectively. The highest stability with initial decomposition temperature (253°C) and percentage residual at 500°C (11.4%) was achieved with an aliphatic‐based RSO polyurethane. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of polyurethane anionomers

Un‐ionized polyurethane was obtained by the reaction of an isocyanate‐terminated urethane prepolymer, which was synthesized from 4,4′‐diphenylmethane diisocyanate and poly(oxytetramethylene)‐α,ω‐glycol, with 2,2‐bis(hydroxymethyl)propionic acid. A carboxylate‐based polyurethane anionomer was then derived from the polyurethane by the use of the sodium, potassium, or magnesium salt of acetic acid as a neutralizer. The ionomerization resulted in the following changes in the characteristics of the polyurethane: (1) an increase in the tensile strength, (2) a decrease in the glass‐transition temperature, (3) an increase in the wettability and hygroscopicity with respect to water, and (4) susceptibility to thermal decomposition. A sulfonate‐based polyurethane was also synthesized for comparison with the carboxylate‐based polyurethane. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2144–2148, 2005     

高固含量聚醚型水性聚氨酯的合成与影响因素

以异佛尔酮二异氰酸酯(IPDI)和六次甲基二异氰酸酯(HDI)为硬段、聚醚(N-220)为软段,二羟甲基丙酸(DMPA)为亲水性物质、乙二胺为后扩链剂和三羟甲基丙烷(TMP)为交联剂等,合成了高固含量的聚醚型水性聚氨酯(WPU)乳液。采用衰减全反射红外光谱(ATR)对其结构进行了表征,并探讨了溶剂(丙酮)和DMPA含量、反应过程中预聚体的黏稠度、扩链剂的加料顺序和扩链时间等因素对WPU乳液固含量的影响。实验结果表明,在保持其他条件不变的情况下,即n(-NCO)∶n(-OH)=1.2∶1、m(HDI)∶m(IPDI)=2∶1和n(TMP中-OH)∶n(聚醚中-OH)=1∶4、w(DMPA)=1.5%(相对于树脂而言)且w(丙酮)=50.4%～75.5%(相对于树脂而言)时,在预聚反应过程中,若体系较稀(即黏度较低),在乳化时先加入乙二胺,待反应4～7min后再加入水,如此易制得稳定的高固含量(40%～46%)聚醚型WPU乳液。     

Mechanical properties of crosslinked polyurethane elastomers based on well‐defined prepolymers

This article presents research findings for selected mechanical properties of polyurethane elastomers. The studied elastomers were synthesized with the prepolymer‐based method with the use of controlled molecular weight distribution (MWD) urethane oligomers and with the classical single‐stage method. Prepolymers with defined MWDs were obtained with the use of a multistage method, that is, step‐by‐step polyaddition. To produce elastomers, isocyanate oligomers were then crosslinked with triethanolamine, whereas hydroxyl oligomers were crosslinked with 4,4′,4′′‐triphenylmethane triisocyanate (Desmodur RE). The tensile strength of the obtained elastomers ranged from 1.0 to 7.0 MPa, the ultimate elongation approached 1700%, the Shore A hardness varied from 40 to 93°, and the abrasion resistance index fell within 15–140. The effects of the types of raw materials used, the chemical structures, the production methods, and the supermolecular structures on the mechanical properties of the obtained polyurethane elastomers were examined. When the obtained findings were generalized, it was concluded that the structural changes in the polyurethanes, which were favorable for intermolecular interactions, improved the tensile strength, hardness, and abrasion resistance of the materials and impaired their ultimate elongation at the same time. More orderly supermolecular structures and, therefore, superior mechanical properties were found for polyurethane elastomers produced with the prepolymer method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyglycidyl nitrate (PGN)‐based energetic thermoplastic polyurethane elastomers with bonding functions

PGN‐based ETPUEs were synthesized using mixture of chain extenders including 1, 4‐butanediol and Diethyl Bis(hydroxymethyl)malonate (DBM). Through the special chain extenders DBM, the –COOR was introduced into the energetic thermoplastic polyurethane elastomers (ETPUEs) and further enhances the adhesion between ETPUE and nitramine solid ingredients in propellants. From the analysis, with the percentage of DBM increasing, the work of adhesion (W_a) between nitramine solid ingredients and ETPUEs increased and the maximum stress (σ_m) of ETPUEs decreased on the other hand. In order to test the bonding functions of different ETPUEs, the RDX/ETPUE propellants were prepared and the stress–strain curves of all propellants were tested. The results showed that the ETPUE‐75 with 75% DBM can prevent the dewetting and improve the mechanical properties of propellants. The ETPUE prepared with chain extender including 1, 4‐butanediol and DBM were valuable for application in propellants. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42026.     

Synthesis and characterization of biodegradable polyurethanes based on L‐cystine/cysteine and poly(ϵ‐caprolactone)

Tunable biodegradable polyurethanes (PUs) with favorable mechanical properties were synthesized from 1,6‐hexamelthylene diisocyanate (HDI) as the hard segment, poly(?‐caprolactone) (PCL) as the soft segment, and L ‐cystine ester as chain extender. The structure of PUs was confirmed by FTIR and ¹H‐NMR. The results of differential scanning calorimeter, thermogravimetric analysis, dynamic mechanical analysis, and tensile test revealed that the thermal and mechanical properties of PUs were strongly influenced by the molecular weight of soft segment PCL. In the presence of glutathione, the disulfide group cleaved into thiols, realizing the PUs degraded and the molecular weight decreased. For PU [550], it remained only 50% of the original M_w. Evaluation of cell viability demonstrated the nontoxicity of the PUs, which facilitated their potential in biomedical applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Functional polymer from high molecular weight linear polyols and polyurethane‐based crosslinking units: Synthesis,characterization, and boron retention properties

The objective of this work was to synthesize functional polymers, with boron removal properties, from high molecular weight linear polyols based on N‐methyl‐d ‐glucamine (NMDG) and polyurethane units as crosslinking reagent. For that, (4‐vinylbenzyl)‐N‐methyl‐d ‐glucamine monomer (VbNMDG) was synthesized from vinylbenzyl chloride and NMDG, and subsequently, high molecular weight linear poly(VbNMDG) was obtained by radical free polymerization. Later, polymer dots were obtained from poly(VbNMDG) and urethanization reactions using methylene diphenyl diisocyanate at room temperature. Monomers and polymers were characterized by different techniques (FTIR, DLS, elemental analysis, H¹‐NMR). In addition, boron retention properties were studied by diafiltration technique using the azomethine‐H method. It was concluded that synthesis of polymer dots, with high boron retention capacity, can be easily synthesized by procedure described. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43895.     

Preparation and characterization of polyurethane/silica aerogel nanocomposite materials

In this investigation, silica aerogel (SA)/Rigid Polyurethane (PUR) foam composites and silica aerogel/Polyurethane (PU) composites were prepared by dry mixing of granular and grinded silica aerogels with polyol part. They were then combined with diisocyanate part. Three different types of PUR foams and an elastomeric coating grade of PU were studied as well. Results show that thermal conductivity of foams did not decrease by adding silica aerogel. It even increased for some grades which is assumed to be due to the change in cell configuration of these foams. It was also found that sound insulation performance of these cellular composites did not improve significantly. Unlike foam composites, addition of silica aerogel into elastomeric PU improved its thermal and acoustic insulation properties. Because of the more promising properties of elastomeric PU composites, further examinations including measurements of compression strength and water contact angle of silica aerogel/PU composites were also taken. Final results showed a significant improvement in general properties of PU coatings by adding little amounts of silica aerogel (1–4 wt %). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44521.     

Lignin‐xylaric acid‐polyurethane‐based polymer network systems: Preparation and characterization

Polyurethanes (PU) were synthesized from lignin by first preparing a prepolymer from esterified sugar‐based trihydroxyl compound xylaric acid and a 20 mol % excess of methylene diphenyl diisocyanate. The prepolymer was crosslinked with 5, 10, and 15 wt % of an industrial soda lignin, and polyethylene glycol was used to bring soft segments into the material structure. The total amount of bio‐based starting materials was as high as 35%. Evidence for the reaction between the prepolymer and lignin was observed using Fourier transform infrared spectroscopic analysis and ¹³C nuclear magnetic resonance spectroscopy. The thermal properties of the materials were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The mechanical and viscoelastic properties of the materials were determined by dynamic mechanical analysis (DMA). The glass transition temperatures (T_g) obtained from DSC and DMA showed a trend of increasing T_g with the increasing amount of lignin. A similar trend was observed with TGA for the increasing thermal stability up to 550^oC with the increasing amount of lignin. The lignin‐polyurethanes obtained were stiff materials showing high Young's modulus values. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39714.     

Evaluation by various experimental approaches of the crosslink density of urethane networks based on hydroxyl‐terminated polybutadiene

Crosslink density (CLD) is an important characteristic for elastomeric polymer networks. The mechanical and viscoelastic properties of the elastomers are critically dependant on the CLD. Several methods have been adopted for its determination, but swelling and stress–strain methods continue to be more popular because of the convenience associated with these techniques. In this article, the determination of CLD of allophanate–urethane networks based on hydroxyl‐terminated polybutadiene and toluene diisocyanate with swelling and stress–strain methods is reported. The Flory–Rhener relationship was applied to calculate CLD from the swelling data. CLDs were also calculated from the initial slope of the stress–strain curve (Young's modulus), Mooney–Rivlin plots, equilibrium relaxation moduli, and dynamic mechanical properties. A comparison was drawn among the values obtained with the various methods. Although the CLD values obtained from Mooney–Rivlin plots were slightly lower than those obtained from swelling data, the values obtained with Young's modulus and storage modulus were considerably higher. The values obtained with swelling and equilibrium relaxation moduli data were very close to each other. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3129–3133, 2007