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     

Crosslinking of unfilled carboxylated nitrile rubber with different systems: Influence on properties

The presence of two functional groups, nitrile and carboxyl, in carboxylated nitrile rubber allows it to be crosslinked with different agents. In this study, we examined the influence of different crosslinking agents on the properties of unfilled carboxylated nitrile rubber. Significant differences were found when different crosslinking agents were used, as shown in the vulcanization curves, especially in the variation of the viscous component with the reaction time. The reaction rate was highest when organic peroxide was used, and it was lowest when metallic peroxide or copper sulfate was used. When the crosslinking agents led to the formation of ionic bonds (metallic oxide and metallic peroxide), the carboxylic groups ? COOH had a greater participation in the crosslinking. However, when copper sulfate was used, coordination bonds were formed, and the main contribution was due to the nitrile groups. Tensile strength, tear strength, and abrasion properties were superior when the crosslinking systems used led to the formation of ionic bonds. On the contrary, the compression set was optimum when covalent bonds were formed. Copper sulfate behaved as an intermediate between the two previous situations. The mechanodynamic response of the compounds also depended on the crosslinking agent used. The correlation between crosslink density by swelling in dichloromethane, maximum damping temperature by dynamic measurements, and glass‐transition temperature by differential scanning calorimetry had to be explained in terms of the crosslink type. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of hybrid urethane polymers containing polyhedral oligomeric silsesquioxane crosslinker

The synthesis and properties of novel hybrid silsesquioxane‐containing urethane polymers using octakis(hydroxypropyldimethylsiloxy)octasilsesquioxane (OHPOSS) as a crosslinker and a hydroxyl‐terminated polybutadiene were studied. Mixing of the OHPOSS with polyurethane prepolymer and chain extenders in solution was found to be successful when tetrahydrofuran was used as the solvent. Thin films of hybrid polyurethanes were obtained. The hybrid materials were elastomers with improved water and solvent resistivity and good thermal stability. The studied OHPOSS appeared to be an effective crosslinker of polyurethanes suitable for, for example, surface coatings applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2023–2030, 2013     

Mechanical and thermal properties of polyurethane elastomers based on hydroxyl‐terminated polybutadienes and biopitch

Biopitch is a renewable source of polyol obtained from Eucalyptus tar distillation, which was studied as an active component of polyurethane (PU). The polymerization occurred in one step, with a mixture of biopitch and hydroxyl‐terminated polybutadiene polyols reacted with 4‐4′‐diphenyl methane diisocyanate in the presence of dibutyltin dilaurate. Solid‐state ¹³C‐NMR, IR spectroscopy, elemental analysis, and thermal analysis [thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)] were used to characterize the biopitch. The biopitch sample showed an aromatic and oxygenated structure with great thermal stability at high temperatures. Multiphasic PUs were synthesized and characterized by IR spectroscopy (attenuated total reflectance), elemental analysis, thermal analysis (TGA and DSC), mechanical assays (tensile strength, elongation at break, toughness, hardness, and resilience), and water absorption resistance (ASTM D 570‐81). In a comparative study of the synthesized elastomers, biopitch content increased tensile strength and hardness and decreased thermal stability, elongation at break, and water absorption. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 759–766, 2003     

Crosslinking of natural and polybutadiene rubbers with thiuram sulfur donors in the presence of a thiuram monosulfide

The influence of tetramethylthiuram monosulfide (TMTM) in the vulcanization process of natural rubber and butadiene rubber with dipentamethylene thiuram tetrasulfide (DPTT) was investigated. Vulcanization parameters as reaction rate and reversion varied when TMTM was added in NR‐DPTT formulations. Crosslinking density and proportion of monosulfidic crosslinks increased with TMTM content increase. However, a drop in physical properties was observed at high TMTM content and at long times of curing well over t₉₇. Formation of densely crosslinked areas due to polymerization reaction was postulated as the origin of these variations. In BR‐DPTT compounds, torque and monosulfidic crosslink proportions increased when TMTM was added. Polymerization reaction takes place in BR systems too. However, in BR vulcanizates, C—C bonds decreased with TMTM proportion, whereas in NR vulcanizates increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1756–1761, 2004     

Morphology,crystalline features,and tensile properties of syndiotactic polypropylene blends

Syndiotactic polypropylene (sPP) was modified with ethylene–octene copolymer (EOC) and ethylene–propylene rubber (EPR), with test samples prepared in a twin‐screw extruder and then injection‐molded. The phase morphology, rheology, and thermal and tensile properties of the modified sPP were investigated. Atomic force microscopy studies showed how the phase morphology of the sPP blends with elastomers depended on the blend compositions, and the results compared with the storage modulus at low frequency. EOC and EPR were dispersed phase in an sPP matrix with spherical shapes when the dispersed content was 20 wt % or lower. The phase cocontinuity started around 40 wt % EOC for the sPP–EOC blends and around 60 wt % EPR for the sPP–EPR. The dispersed phase then formed more complex elongated shapes. The rheological and thermal properties were affected by the sPP–elastomer interphase. EOC promoted the crystallization of sPP; this increased the crystallization temperature and rate. In contrast, EPR had the opposite effect on the crystallization behavior, and the results indicate that sPP and EPR were not completely separated. The tensile properties were studied from ?20 to 100 °C. We found that the tensile properties at low temperature could be improved without a loss in high‐temperature properties. In the particular case of 20 wt % EOC, both the strain at yield and strain at break of the sPP–EOC blend were improved at both ?20 and 100 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44611.     

A novel polyurethane sealant based on hydroxy‐terminated polybutadiene

A novel two component polyurethane sealant has been prepared. Component A, known as prepolymer, is synthesized by capping hydroxy‐terminated polybutadiene (HTPB) with toluene diisocyanate. Component B, known as hardener, comprises of a polyol (polyoxypropylene triol) as crosslinker and 4,4′‐diamino‐3,3′‐dichlorodiphenylmethane (DADCDPM) and 4,4′‐diamino‐3,3′‐dichlorotriphenylmethane (DADCTPM) as chain extenders and fillers. Evaluation of mechanical properties and aging studies indicate that the sealant has excellent mechanical properties and stability in different environment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 884–890, 2006     

Vulcanization of polybutadiene rubber with dipentamethylene thiuram tetrasulfide

The cure of polybutadiene rubber (BR) with sulfur donor dipentamethylene thiuram tetrasulfide (DPTT) does not show reversion reaction, in contrast with similar natural rubber compounds. No polysulfure links are formed; whereas a great amount of ? C? C? crosslinks are produced. The addition of tetramethyl thiuram monosulfidic (TMTM) strongly affects the crosslinking process. Mechanical properties of the cured compounds are poor. In DPTT, curing of BR the radical species produced through homolitic cleavage of DPTT molecule seems to have sufficient energy to produce crosslinking, via allylic abstraction, and also initiate the polymerization of double bonds producing areas of high crosslinking density that induce early material failure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 106: 3481–3487, 2007     

Safe amine based zinc dithiocarbamates for the vulcanization of carbon black reinforced natural rubber

Binary combination of three safe amine based synthesized zinc dithiocarbamates (ZDC), namely zinc (N‐benzyl piperazino) dithiocarbamate (ZBPDC), zinc (N‐ethyl piperazino) dithiocarbamate (ZEPDC), and zinc (N‐phenyl piperazino) dithiocarbamate (ZPPDC) with mercapto benzothiazole disulfide (MBTS) as an effective accelerator system for the vulcanization of carbon black (N330, N550, and N774) filled natural rubber (NR) composites are studied. A comparison between the safe amine based zinc dithiocarbamates with the unsafe zinc dimethyl dithiocarbamate (ZDMC) in the light of mechanical and aging resistance behavior, introduces the non carcinogenic rubber additives in the filled vulcanization of rubber. Both accelerator and filler have the major importance for improving the mechanical as well as aging resistance behavior of the resultant vulcanizate. Variation in the filler and also filler to oil ratio are done to optimize the mechanical properties. SEM studies of different types of filler with different amounts show that N330 at 30 phr loading composites forms more homogeneity and less aggregated structures. Natural rubber systems with N330 carbon black show the best results with respect to tensile strength, but after the aging N774 carbon black filled system indicates better retention in the tensile strength. ZPPDC‐MBTS accelerated vulcanizate shows the better age resistance behavior than ZDMC‐MBTS accelerated vulcanizate. From both the points of age resistance and mechanical properties, ZBPDC‐MBTS accelerator system is the suitable substitute for ZDMC‐MBTS accelerated system in the filled vulcanization of natural rubber composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39988.     

Aspects of varying crosslinker and catalyst concentrations on tear strength of silicone polymer networks: Comparison of tear strengths using samples of different geometries

Crosslinker and catalyst concentrations have been varied to prepare different hydroxyfunctional poly(dimethylsiloxane) (HOPDMS) polymer network compositions. The tear strengths of these silicone polymer networks have been measured using different geometries, as trouser, crescent, and Graves (angled) specimens. It has been observed that the results of tear strength of Graves and crescent‐shaped specimens do not show a constant ratio with the concentration of crosslinker used for curing of HOPDMS networks. Instead, it has been observed and reported for the first time that the tear strengths of Graves and crescent‐shaped samples show a crossover at about 1.2% crosslinker. The observation of this crossover pattern for different compositions of silicone networks show that it is difficult to compare the results of the tear test of the same polymer performed on samples of different geometries with one another. The crossover pattern of the tear energy results for the test specimens of two different geometries has been explained in the light of essential work facture theory based on the geometry of the testing sample, crosslinking, and testing that alters the distribution of force over the width of the specimen. It was shown that the change in composition of the HOPDMS networks changes the order of ranking of Graves and crescent tear tests. With varying catalyst concentration in the silicone network composition, the tear property differences between the Graves and crescent‐shaped specimens are not significant. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43115.     

Preparation,hydrogen bonding and properties of polyurethane elastomers with 1,2,3-triazole units by click chemistry

Two kinds of diols containing 1,2,3-triazole units were synthesized through the azide-alkyne cycloaddition reaction between propargyl alcohol and 1,4-diazidobutane. One of the diols, (butane-1,4/1,5-diylbis[1H-1,2,3-triazole-1,4/1,5-diyl])dimethanol (BDTDO-1), containing 1,4/1,5-disubstituted 1,2,3-triazole regioisomers, was directly prepared under thermal condition without Cu(I) catalyst. The other diol, (butane-1,4-diylbis[1H-1,2,3-triazole-1,4-diyl])dimethanol (BDTDO-2), containing 1,4-disubstituted 1,2,3-triazoles, was prepared by Cu(I) catalyzed click chemistry. Then, two kinds of 1,2,3-triazole modified polyurethane elastomers (PUEs) were prepared from the reaction of 4,4′-methylenebis(phenyl isocyanate) and poly(tetramethylene ether) glycol, with BDTDO-1 or BDTDO-2 as the chain extender (CE). It was found that the introduction of 1,2,3-triazoles and their substitution positions had significant influences on the hydrogen bonding, thermal and mechanical properties of PUEs. Compared with the PUE prepared from 1,4-butanediol as the CE, the PUE containing symmetric 1,4-disubstituted 1,2,3-triazoles units in the main chains shows higher values of hydrogen bonding, physical crosslinking density, Young's modulus, tensile strength and melting temperature, while lower glass transition temperature, resulting from the rigid structure and the ability to form more hydrogen bonds. However, the introduction of asymmetric 1,4/1,5-disubstituted 1,2,3-triazole moieties decreases the values of hydrogen bonding, thermal and mechanical properties of PUE appreciably due to the destruction of the ordered structure of the hard segments.     

Structure and properties of polyurethane acrylate prepolymers based on hydroxy‐terminated polybutadiene

Precursors of polyurethane acrylate based on hydroxy‐terminated polybutadiene (HTPB) soft segments, different diisocyanate and hydroxy ethyl acrylate (HEA) as hard units, were synthesized in bulk or in solution in methyl methacrylate. During precursor synthesis (in bulk), microphase separation was observed by small‐angle X‐ray scattering (SAXS). Diffusing particles are around 50 Å in size and are assumed to be assembling of hard segments. From these morphologies, it can be deduced that some isocyanate groups were trapped/or buried in hard domains. At a larger scale, around millimeters, hard segment crystallites were observed. Properties such as molar masses, melting and glass‐transition temperatures, and viscosities were correlated with precursor structure and morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 225–233, 2002     

Morphology and mechanical properties of urethane acrylate resin networks

A series of urethane acrylate resins (UARs) having various amounts of hard segment were synthesized from poly(oxypropylene) diols (PPOs) with different molecular weights and characterized. The relationship between the morphologies and mechanical properties of these UAR (UARX‐Y‐Z, in which X means the molecular weight of PPO, Y means the content of hard segment, and Z means the content of comonomer) networks was investigated in detail. It was found that the morphology of the UARX‐Y‐Z network was related to the contents of hard segment and the comonomer (methyl methyacrylate—MMA) as well as the molecular weight of PPOs. The UAR1000‐0‐34 network synthesized from PPO210(M_n = 1000) is a homogeneous system due to the good compatibility between the PPO210 and the MMA segment. TheUAR1000‐0‐60 network exhibits the morphology of partial microphase separation resulting from increasing the length of the MMA segment, so as to decrease the miscibility between the soft and hard segment. For the UAR1000‐30‐34 network having a higher content of the hard segment, the hard segments tend to form domains with the limited short‐range and long‐range order, leading to the formation of the microcrystallites, and therefore it shows higher tensile strength and elastic modulus. For UAR400‐0‐34 network with lower molecular weight PPO204 (M_n=400), a high glass transition temperature and some microcrystallites were observed. Such a network exhibits the best mechanical properties over all UAR networks studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1532–1537, 2000     

Effect of mica addition on the properties of natural rubber and polybutadiene rubber vulcanizates

The rheometric, mechanical, and dynamic mechanical properties as well as fracture surfaces of natural rubber–mica and polybutadiene rubber–mica vulcanizates were studied. Mica was used in the range of 0–30 phr and the rheometric study was carried out at 160°C. The results indicate that the mechanical properties are improved as filler addition increases. Dynamic mechanical testing was used to analyze the observed mechanical behavior. The two elastomers showed different fracture behaviors. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2156–2162, 2003     

Morphology and mechanical properties of dual‐curable epoxyacrylate hybrid composites

A dual‐curable epoxyacrylate (EA) oligomer with one epoxide group and one vinyl group at each end was synthesized for the application as adhesive sealant in the liquid crystal display panels. However, after UV and thermal cure, the EA resin was brittle with a poor resistance to crack initiation and propagation. Liquid rubbers with different functional end groups were thus tried as toughening agents for the EA resin. Among all the rubber‐toughened EAs, the EA‐V5A5 added with vinyl‐terminated and amino‐terminated butadiene‐acrylonitrile copolymers (VTBN and ATBN) each at 5 phr had the highest fracture toughness, tensile strength, and elongation at break but a lower initial modulus. To raise the modulus, submicron‐sized silica particles (∼170 nm) with surface vinyl functional groups were further added to the EA‐V5A5 to prepare the hybrid composites. Because of interfacial chemical bonding provided by the surface vinyl functional groups, both modulus and fracture toughness were increased by adding silica particles, without any appreciable decrease in extensibility. For the hybrid composite at 20 phr silica particles, the initial modulus, fracture toughness, and fracture energy were raised by 10.3, 100, and 267%, respectively, when compared to the neat epoxyacrylate. Owing to their strong interfacial bonding, the increase of fracture toughness was mainly due to the crack deflection and bifurcation on silica particles, in addition to the rubber particle bridging and tearing as evidenced by SEM pictures on the fracture surface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41820.     

Influence of 1,2‐polybutadiene on properties of dicumyl peroxide cured brominated butyl rubber

Peroxide curing of brominated butyl rubber (BIIR) is an attractive topic, but the degradation of BIIR during the curing is a drawback needed to be overcome. Coagent assisted peroxide curing system is an attractive and effective choice in order to increase the crosslink density of rubbers. 1,2‐polybutadiene (1,2‐PB) is used as a crosslinking coagent for the curing of BIIR by dicumyl peroxide (DCP), and the effect of 1,2‐PB on the curing characteristics, crosslink density, and mechanical properties is investigated. The addition of 1,2‐PB affects the curing characteristics of BIIR compound and significantly increases the crosslink density of BIIR vulcanizates. With increasing 1,2‐PB content, the tensile strength and stresses at a given extension of BIIR vulcanizates increase, but the elongation at break decreases. A stress‐softening effect of the carbon black filled BIIR vulcanizates is observed and becomes more pronounced with increasing 1,2‐PB content. The addition of 1,2‐PB increases the stress relaxation index of BIIR. GPC and ¹³C‐NMR results indicate 1,2‐PB participates in the crosslinking reaction, and the existence of 1,2‐PB component in the insoluble fraction of BIIR/1,2‐PB vulcanizates is confirmed by solid‐state ¹³C‐NMR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43280.     

Influence of morphology on the dynamic mechanical properties of hydrogenated acrylonitrile butadiene elastomer/coagent nanodispersions

Coagents are vinyl monomers that react with free radicals formed by peroxide dissociation and are either grafted to elastomer chains or homopolymerized within a segregated phase to form a crosslinked network. The initial phase distribution within the elastomer matrix is of great importance for the final user properties of a composite material. In this study, the morphology of blends of each of three different coagents, that is, zinc dimethacrylate (ZDMA), N,N′‐m‐phenylene dimaleimide (HVA‐2), and trimethylolpropane trimethacrylate (TMPTMA) on a reinforcing substrate with dicumyl peroxide and hydrogenated acrylonitrile butadiene elastomer after processing was investigated with scanning electron microscopy. The morphology that evolved during processing was then compared to the results obtained from dynamic mechanical analysis (DMA) of the blends. Dynamic mechanical properties were modeled with a continuous relaxation distribution function, the Williams–Landel–Ferry equation, and the modified Guth–Gold equation. In the case of ZDMA and TMPTMA, a microphase and a nanophase evolved during processing, whereas the HVA‐2 phase in the blends remained well segregated. The volume fraction of the particles under 100 nm in ZDMA and TMPTMA blends ranged from 79 to 89%. The DMA results revealed the reinforcing effect of ZDMA and TMPTMA during the glass‐transition and in the plateau region, whereas HVA‐2 exhibited plasticizer‐like behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

Influence of urethane group on properties of crosslinked polyurethane elastomers

Three series of weakly crosslinked polyurethanes based on a hydroxyterminated polybutadiene, hydroxyterminated butadiene–acrylonitrile copolymer, and hydroxyterminated ethylene–adipate–maleate–fumarate copolymer were prepared while varying the hard segment content between 1.72 and 2.36 mol ? NH? COO? /1000 g polymer. Information on the microphase structure and the properties of the synthesized polyurethanes was obtained by differential scanning calorimetry, wide‐angle X‐ray scattering, and mechanical studies. Up to a urethane concentration of around 2 mol ? NH? COO? /1000 g polymer, there is a mixture of hard–hard and hard–soft segments. Above this concentration a large part of the hard–soft segments passes into hard–hard crystallites, liberating the soft segments. The best mechanical properties of the studied polyurethanes were found for a urethane concentration of around 2 mol ? NH? COO? /1000 g polymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1858–1867, 2003     

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