Crosslinking and mechanical property of liquid rubber. II. Curative effect of aromatic diols

The relationships between the properties and structure of polyurethane elastomers derived from hydroxyl-terminated liquid polybutadiene (HT-BD), several low molecular weight aromatic diols, and diisocyanates were studied. The curative effects of the diols were examined by such means as tensile properties, dynamic viscoelasticity, x-ray diffraction, and others. It was found that the properties of the elastomers derived from HT-BD were greatly affected by the structure of low molecular weight chain extender diol. These results were interpreted by the steric effect, crystallinity, and the concentration of polar groups.     

Polyurethane elastomers containing polybutadiene and aliphatic diols: Structure-property relationships

The effect of aliphatic diols on the structure and some mechanical properties of polyurethane elastomers containing hydroxyl-terminated polybutadiene and three different diisocyanates was studied. Differential scanning calorimetric studies revealed the existence of several thermal transitions, characteristic of structures of multiphased elastomers. Three transition temperatures, a subzero transition and two high temperature transitions, were found in some of the elastomers. The higher-high temperature transition reflects ordered domains, also supported by X-ray diffraction, Higher degree of order was achieved with longer diols. The mechanical behavior is affected by the multiphase nature of the elastomers, especially by the morphology of the hard segment domains. The structureproperty relationships for the three component polyurethane elastomers in question thus have been established.     

对苯二异氰酸酯型聚氨酯弹性体的合成及性能研究

以对苯二异氰酸酯(PPDI)、低聚物多元醇和小分子二元醇等为原料合成了PPDI浇注型聚氨酯弹性体,考察了不同低聚物多元醇对弹性体的物理机械性能、动态力学性能及热氧老化性能的影响,并与MDI和TDI型聚氨酯弹性体进行了比较。结果表明,PPDI型聚氨酯弹性体较MDI、TDI型弹性体具有更低的内生热、更高的回弹性,可用于轮胎胎面材料的制备。     

Chain-extended polyurethanes—Synthesis and characterization

Thermoset polyurethane (PU) elastomers were prepared using hydroxyl-terminated polybutadiene (HTPB), toluene diisocyanate (TDI) and hexamethylene diisocyanate (HMDI). The effects of various diamines and diols on the mechanical and thermal properties of polyurethanes are discussed. The average molecular weight between crosslinks (M?/_c) was determined by swelling studies. The properties imparted by the extenders are explained on the basis of the groups present in the diamines and the number of methylene carbons in the diols.     

Mechanical properties and fractography of block copolymers based on NR and MDI-based polyurethanes

Five series of block copolymers were synthesized from hydroxyl-terminated liquid natural rubber (HTNR) and polyurethane (PU) oligomers, from various diols and diphenyl methane-4,4′-diisocyanate (MDI). They were characterized by mechanical testing and fracture studies (SEM analysis). The block copolymer characteristics were assessed on the basis of the composition and the type of extender diols. Mechanical properties were found to be strongly dependent on the copolymer composition in all the series. Tensile properties were found to improve with the hard segment content. At low hard segment content samples resemble flexible elastomers whereas at high hard segment content they behave as rigid plastics. Where bisphenol A (BPA) is used as the extender diol sample rigidity was higher compared to the samples with aliphatic diols which is attributed to the presence of aromatic ring system in the former samples. Fracture mechanism was found to vary from ductile fracture to rigid and brittle fracture as the hard segment content increased. Fractography also shows the presence of some beads disposed on the sample surface which could be the uncombined polyurethane homopolymer fractions.     

Effects of low molecular weight aliphatic diols on the polyurethane elastomers prepared from hydroxyl-terminated polybutadienes

Hydroxyl-terminated polybutadienes were prepared by using azo initiators such as di(4-hydroxybutyl)-2,2′-azobisisobutyrate and di(3-hydroxybutyl)-2,2′-azobisisobutyrate, one of which contains primary and the other secondary hydroxyl groups. The effects of aliphatic diols and 2,4-toluene diisocyanate (TDI) in the presence of dibutyltindilaurate (DBTDL) as catalyst, on crosslinking of primary and secondary hydroxyl groups, were studied. Polyurethane elastomers from these polymers are prepared by using different ratios of diols, 2,4-toluene diisocyanate and catalyst. Physical properties such as hardness, tensile strength, 100% modulus, and elongation at break of these polymers were studied with a view to compare them with the physical properties of elastomers prepared from ARCO R-45M.     

Thermoplastic polyurethane–urea elastomers with superior mechanical and thermal properties prepared from alicyclic diisocyanate and diamine

High-performance thermoplastic polyurethane (TPU) elastomers have long been the objective of numerous studies. In this work, thermoplastic polyurethane–urea (TPUU) elastomers with balanced superior mechanical and thermal properties, in comparison with the rare cases of high-performance TPU/TPUU elastomers with super-high tensile strength, were synthesized by the reaction of polycarbonate diols with excess alicyclic isophorone diisocyanate, followed by the chain extension of alicyclic isophorone diamine. When the content of hard segment was around 47%, the TPUU elastomer had super-high tensile strength of 51.7 MPa, initial elastic modulus of 698 MPa and elongation at break of 480%. The temperature range of this TPUU elastomer's rubbery state was up to 120°C with storage modulus above 200 MPa, and its rubbery flow state reached 200°C where the storage modulus was still as high as 100 MPa. Fourier transform infrared spectroscopy analysis indicated the presence of strongly hydrogen bonded urethane and urea groups in these TPUU elastomers. Atomic force microscopy and differential scanning calorimetry studies demonstrated significant and nearly perfect microphase separation in these TPUU elastomers when the hard segment content was around or below 47%. These noncrystalline TPUU elastomers could be thermally processed or processed in the form of a solution.     

Development and long-term in vivo evaluation of a biodegradable urethane-doped polyester elastomer

We have recently reported upon the development of crosslinked urethane-doped polyester (CUPE) network elastomers, which was motivated by the desire to overcome the drawbacks presented by crosslinked network polyesters and biodegradable polyurethanes for soft tissue engineering applications. Although the effect of the isocyanate content and post-polymerization conditions on the material structure-property relationship was examined in detail, the ability of the diol component to modulate the material properties was only studied briefly. Herein, we present a detailed report on the development of CUPE polymers synthesized using diols 4, 6, 8, 10, or 12 methylene units in length in order to investigate what role the diol component plays on the resulting material's physical properties, and assess their long-term biological performance in vivo. An increase in the diol length was shown to affect the physical properties of the CUPE polymers primarily through lowered polymeric crosslinking densities and elevated material hydrophobicity. The use of longer chain diols resulted in CUPE polymers with increased molecular weights resulting in higher tensile strength and elasticity, while also increasing the material hydrophobicity to lower bulk swelling and prolong the polymer degradation rates. Although the number of methylene units largely affected the physical properties of CUPE, the choice of diol did not affect the overall polymer cell/tissue-compatibility both in vitro and in vivo. In conclusion, we have established the diol component as an important parameter in controlling the structure-property relationship of the polymer in addition to diisocyanate concentration and post-polymerization conditions. Expanding the family of CUPE polymers increases the choices of biodegradable elastomers for tissue engineering applications.     

Crosslinking studies of polyether–ester-based polyurethane systems

Ether- and ester-based prepolymeric diols suitable for polyurethane elastomer formation were prepared from polyoxytetramethyleneglycol and polyoxytetramethylene–oxypropyleneglycol with dicarboxylic acids like adipic acid, maleicacid, and phthalic acid. Crosslinked polyurethane elastomers were prepared from these prepolymers using various concentrations of trimethylolpropane as a crosslinker and toluenediisocyanate as the curing agent. Crosslinked polyurethanes were also prepared by a method taking excess toluenedisocyanate other than that of the stochiometric requirement and curing it at a comparatively higher temperature. The data on mechanical properties of these elastomers show that both methods of crosslinking in polyurethane imparts a similar effect on mechanical properties.     

Polyätherester-Block-Copolymere – Eine Gruppe neuartiger thermoplastischer Elastomerer

High melting polyether esters can be prepared by ester interchange from readily available starting materials such as dimethyl terephthalate, polyalkylene ether glycols and linear short chain diols. The resulting block copolymers exhibit a continuous two-phase domain structure consisting of amorphous polyether ester soft segments and crystalline short chain polyester hard segments. By proper selection of the relative amounts of polyether and polyester segments, polymers ranging from fairly soft elastomers to impact resistant elastoplastics may be obtained. The preparation, morphology and physical characterization of polyether esters as well as the effect of the structures of the soft and hard segments on polymer properties are described. Polytetramethylene terephthalate based on polyether esters are particularly suited as thermoprocessable high performance elastomers offering an unusual combination of physical and chemical properties characterized by high abrasion, tear and solvent resistance as well as excellent low and high temperature properties. Because of their good melt stability, low melt viscosity and high crystallization rates, these polymers can be processed within a wide temperature range by all methods commonly used in the plastics industry.     

Thermoplastic urethane elastomers. I. Effects of soft-segment variations

A series of thermoplastic urethane elastomers with soft segments of varying sequence length was prepared and their dynamic mechanical properties were characterized over a wide temperature range. The polymers were prepared using various molecular weight polycaprolactone diols as the soft segment and 4,4′-diphenylmethane diisocyanate and 1,4-butanediol as the hard segment. The urethane elastomer exhibited soft-segment crystallization when a polycaprolactone diol greater than 3000 M?_n was used. The glass transition temperature of these materials progressively shifted to lower temperatures as the chain length of the soft segment was increased. This dependence was interpreted in terms of a molecular weight relationship similar to that associated with amorphous homopolymers. The dynamic mechanical properties of these polyurethanes appear to be consistent with responses observed for compatible copolymers.     

Stress–relaxation properties of segmented polyurethane rubbers

Stress–relaxation behavior of polyurethane elastomers based on two hydroxyl-terminated polyesters: poly(ethylene adipate) and poly(ethylene maleate) was studied. In addition, a polyester-diol consisting of poly(ethylene adipate) and oligo(ethylene terephthalate) blocks, a number of low-molecular-weight diols as chain extenders, and 4,4′-diphenylmethane diisocyanate (MDI) were determined. The elastomers were crosslinked by an excess of MDI and had stiff segments of differing chemical structure and length. Stress–relaxation properties of the elastomers conformed with the three-component Maxwell model, with negligibly small contribution from the fastest relaxation process. The influence of crosslinking density, chemical structure, and stiff segment content on the relative relaxation speed and the parameters of the slow and fast relaxation processes, was examined. The elucidation of the results was based on the morphological models of segmented polyurethanes.     

Low-temperature behavior of polyurethane elastomers

A study of the performance at low temperatures of various polyurethane elastomer systems, prepared from polyether and polyester diols with 2,4-toluene diisocyanate and 4,4′-methylenebis(2-chloroaniline), p,p′-diphenylmethane diisocyanate and 1,4-butanediol, and 4,4′-methylenebis(cyclohexylisocyanate) and methylenedianiline, has shown the polytetramethylene ether diols to impart the best low-temperature behavior to the elastomers. The properties studied were the apparent modulus of rigidity with the Clash and Berg torsional apparatus, the hardness with a Shore D Durometer, and the resiliency with the Bashore Resiliometer.     

The effect of soft‐segment structure on the properties of novel thermoplastic polyurethane elastomers based on an unconventional chain extender

Thermoplastic polyurethane elastomers (TPUs) are now widely used because of their excellent properties that include high tensile and tear strength, and good abrasion, impact and chemical resistance. TPUs are multiblock copolymers with alternating sequences of hard segments composed of diisocyanates and simple diols (chain extenders) and soft segments formed by polymer diols. Commonly used hard segments for TPUs are derived from 4,4′‐diphenylmethane diisocyanate (MDI) and aliphatic diols. The aim of our research was to examine the possibility of obtaining TPUs with good tensile properties and thermal stability by using an unconventional aliphatic‐aromatic chain extender, containing sulfide linkages. Three series of novel TPUs were synthesized by melt polymerization from poly(oxytetramethylene) diol, poly(ε‐caprolactone) diol or poly(hexane‐1,6‐diyl carbonate) diol of number‐average molecular weight of 2000 g mol^?1 as soft segments, MDI and 3,3′‐[methylenebis(1,4‐phenylenemethylenethio)]dipropan‐1‐ol as a chain extender. The structure and basic properties of the polymers were examined using Fourier transfer infrared spectroscopy, X‐ray diffraction, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis, Shore hardness and tensile tests. It is possible to synthesize TPUs from the aliphatic‐aromatic chain extender with good tensile properties (strength up to 42.6 MPa and elongation at break up to 750%) and thermal stability. Because the structure of the newly obtained TPUs incorporates sulfur atoms, the TPUs can exhibit improved antibacterial activity and adhesive properties. Copyright © 2011 Society of Chemical Industry     

New castor oil-based urethane elastomers

Urethane elastomers with a wide range of properties were prepared by reaction of toluene diisocyanate, diphenylmethane diisocyanate or an aliphatic diisocyanate with a series of castor oil derivatives. The castor derivatives included amides prepared by reaction of castor oil with mono- or dialkanolamines, amides of ricinoleic acid with long chain di- and triamines, butanediol diricinoleate and the commercial products-castor oil itself and the monoricinoleates of propylene glycol and pentaerythritol. Elastomers were also prepared from commercial polyether diols for comparison. Properties evaluated include hardness, resilience, tear strength, stress-strain properties, compression set and resistance to water and oil. Particularly high tensile and tear strengths were obtained from the amides. Softer products with good properties were obtained from propylene glycol monoricinoleate and from mixtures of the amides with castor oil or butanediol diricinoleate. Improved products were obtained by the use of diphenylmethane diisocyanate in place of toluene diisocyanate. Presented at the AOCS Meeting, Los Angeles, April 1972. ARS, USDA.     

Synthesis of linear aliphatic polycarbonate macroglycols using dimethylcarbonate

A series of linear aliphatic polycarbonate polyols were synthesized using dimethylcarbonate and a linear alkane diol or specific combinations of linear alkane diols. Polyol synthesis was carried out in a two‐stage process using dimethylcarbonate and a linear alkane diol to prepare a series of homopolymer polycarbonate polyols. Polyol grades were characterized using Fourier transform infrared spectroscopy, gel permeation chromatography, and differential scanning calorimetery techniques. Suitable reaction conditions were developed to yield polycarbonate polyols of number average molecular weight between 700 and 1700. The crystallinity of the polycarbonate polyols was shown to reduce as the molecular weight of the alkane diols used in the polycarbonate synthesis was increased. These polymers offer the potential for use in the synthesis of ether free polyurethane elastomers for biomedical applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New fluorinated thermoplastic elastomers

New fluorinated thermoplastic elastomers (FTE) with perfluoropolyether (PFPE) blocks have been synthesized by reacting a fluorinated macrodiol with aromatic diisocyanates in the presence of a solvent, followed by subsequent chain extension with low molecular weight aliphatic or aromatic diols. Tensile properties measurements and dynamical-mechanical analysis (DMA) have been carried out and the relationship between chemical structure and final properties has been determined. These new thermoplastic fluorinated polyurethanes show an elastomeric behavior over a wide temperature range (between −75 and 100°C), thanks to their multiphase morphology consisting of a continuous fluorinated phase with a very low T_g (−120°C) and a dispersed high melting hydrogenated hard phase, as verified by a calorimetric and dynamic-mechanical analysis. At the same time, some of the outstanding properties of fluorinated oligomers, such as chemical inertness and low surface tension, are retained in the final polymers. Thanks to these characteristics this new class of polymeric materials provides new opportunities for the application of thermoprocessable elastomers in advanced technological fields. © 1996 John Wiley & Sons, Inc.     

Reactive processing of thermoplastic elastomers based on polyamide-6: preparation and characterization

A new class of thermoplastic polyamide elastomers was successfully synthesized by polyaddition reactions between amino-terminated polyamide-6 and different diisocyanate-terminated polyether diols or polyester diols in a Haake torque rheometer. The chemical structure, phase separation, static and dynamic mechanical properties, thermal stability and hydrophilicity of TPAEs were characterized by Fourier transform infrared spectroscopy, differential scanning calorimeter (DSC), tensile tests and dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and water contact angle test methods, in the order given. DSC results showed that these synthesized TPAEs exhibited two obvious endothermic peaks associated with melting transition of soft segments and hard segments. The mechanical results revealed that TPAEs possess outstanding mechanical properties with tensile strength of 22.2–35.9 MPa and the elongation-at-break of 360–467 %. TGA results showed TPAEs can be fabricated by traditional thermoplastic processing method without any decomposition once the processing temperature is below 300 °C. Furthermore, the TPAEs only dissolved in acetic acid and methanoic acid at room temperature, showing TPAEs can be applied to some harsh environment due to excellent organic solvent resistance. Especially, this friendly reactive processing can also be used to handle the environmental problems associated with volatile organic compound emission.     

Effect of fillers on thermal and mechanical properties of polyurethane elastomer

The effects of five different types of fillers on the thermal and mechanical properties of hydroxyl-terminated polybutadiene-based polyurethane elastomers were explored to develop a filled polyurethane elastomeric liner for rocket motors with hydroxyl-terminated polybutadiene-based composite propellants. Two type of carbon black, silica, aluminum oxide, and zirconium(III) oxide were used as filler. Based on the improvement in the tensile properties and the erosion resistance achieved in the first part of the study, an ISAF-type carbon black was selected to be used as the main filler in combination with an additional filler. The second part involves the investigation of polyurethane elastomers containing a second filler in various amounts in addition to the ISAF-type carbon black used as the main filler. In addition to the thermal and mechanical properties, the processability of the uncured polyurethane mixtures were also explored by measuring the viscosity in this second part of the study. The studied fillers do not considerbly change the thermal degradation temperatures and the thermal conductivity of the polyurethane elastomers with a filler content up to 16 wt %. The best improvement in the erosion resistance and tensile strength of the polyurethane elastomers with additional fillers is also achieved when filled with the ISAF-type carbon black, whereas the use of zirconium(III) oxide as additional filler provides almost no improvement in these properties. Viscosity of the uncured polyurethane mixtures increases with the increasing filler content and with the decreasing particle size of the filler. Aluminum oxide-filled elastomers seem to be the most suitable compositions having sufficiently high thermal and mechanical properties, together with the processability of uncured mixtures. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1057–1065, 1998     

高性能聚氨酯弹性体的研究概况

本文介绍了高性能聚氨酯弹性体的研究概况 ,讨论了高分子质量聚醚、PPDI、NDI、HTPB等为主要原料制备的各种聚氨酯弹性体的性能。