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.     

不同无机填料在聚氨酯弹性体中的性能对比

以聚醚N-204、甲苯二异氰酸酯为原料,用1,4-丁二醇为扩链剂,填充经超声波分散、偶联处理的不同无机填料,分别合成填充型聚氨酯(PUR)弹性体。研究了填充型PUR弹性体的耐磨性、力学性能以及填料在弹性体中的分布状况。结果表明,不同无机填料在PUR弹性体中所表现出的性质不同,碳化硅主要提高了弹性体的耐磨性,而陶瓷微珠、玻璃微珠在增强增韧方面发挥了作用。     

Mechanical properties of styrene–butadiene–styrene block copolymer composites filled with calcium carbonate treated by liquid polybutadienes

The factors influencing the mechanical properties of styrene–butadiene–styrene block copolymer (SBS) composites filled with liquid polybutadiene (LB)‐surface‐treated calcium carbonate (CaCO₃) were investigated with respect to the molecular structure of the LB, the amount of the LB adsorbed on the CaCO₃ surface, the heat treatment conditions, and the surface treatment method. The mechanical properties, such as the modulus, tensile strength at break, tear strength, storage modulus, and tension set, of the SBS composites were improved remarkably through the filling of CaCO₃ surface‐treated with a carboxylated LB with a high content of 1,2‐double bonds. The heat treatment of LB–CaCO₃ in air was also effective in enhancing such properties. When SBS, CaCO₃, and LB were directly blended (with the integral blend method), secondary aggregation of CaCO₃ took place, and the mechanical properties of the composite were significantly lower. In the integral blend method, LB functioned as a plasticizer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Aging of HTPB/AP‐based composite solid propellants,depending on the NCO/OH and triol/diol ratios

Aging behavior of hydroxyl‐terminated polybutadiene/ammonium perchlorate (HTPB/AP)‐based composite solid propellants was studied as a function of crosslink density, which is predominantly determined by the molar ratio of diisocyanate to total hydroxyl (NCO/OH ratio) and the molar ratio of triol to diol (triol/diol ratio). For this purpose, 16 propellant samples with different compositions were prepared by changing the NCO/OH ratio as 0.81, 0.82, 0.83, and 0.85 for each triol/diol ratio of 0.07, 0.09, 0.11, and 0.13, and subjected to an accelerated aging at 65°C. The changes in the mechanical properties were monitored throughout the aging period. In the initial part of the aging period, a sharp increase in stress, modulus, and hardness values and a sharp decrease in strain values were observed for all the propellants. At further stages of aging, only slight changes were observed in the mechanical properties. Concerning the aging criterion as reduction in the strain capability more than the half of the initial value, the propellants with respective NCO/OH‐triol/diol ratios of 0.81–0.09, 0.85–0.09, 0.81–0.13, 0.83–0.13, and 0.85–0.13 can be considered to be aged with time. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 959–964, 2001     

组分对高能HTPB推进剂燃烧性能和力学性能的影响

通过调整氧化剂AP粒径与含量、键合剂及R值，研究了固体质量分数为90％的HTPB推进剂的燃烧性能和力学性能。结果表明，在HTPB推进剂能量性能得到提高的同时，推进剂的燃烧性能和力学性能也得到了较好的保证。高固体含量下HTPB推进剂的燃烧和力学性能随配方调节呈现出较为明显的规律。推进剂的燃烧性能稳定，燃速和压力指数可调，压力指数控制在0．30～0．40；分别测定了高温（60℃）、常温（20℃）和低温（-40℃）力学性能，高温、低温和常温下的拉伸强度一般均大于1．0MPa，低温延伸率最高可达74．7％。     

Comparison of properties of thermoplastic polyurethane elastomers with two different soft segments

Two series of thermoplastic polyurethane elastomers [poly(propylene glycol) (PPG) based PP samples and poly(oxytetramethylene)glycol (PTMG) based PT samples] were synthesized from isophorone diisocyanate (IPDI)/1,4-butanediol (BD)/PPG and IPDI/BD/PTMG. The IPDI/BD based hard segments contents of polyurethane prepared in this study were 40–73 wt %. These polyurethane elastomers had a constant soft segment molecular weight (average M_n, 2000) but a variable hard segment block length (n, 3.5–17.5; average M_n, 1318–5544). Studies were made on the effects of the hard segment content on the dynamic mechanical thermal properties and elastic behaviors of polyurethane elastomers. These properties of PPG based PP and PTMG based PT samples were compared. As the hard segment contents of PP and PT samples increased, dynamic tensile modulus and α-type glass transition temperature (T_g) increased; however, the β-type T_g decreased. The permanent set (%) increased with increasing hard segment content and successive maximum elongation. The permanent set of the PT sample was lower than that of the PP sample at the same hard segment content. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1349–1355, 1998     

Polyurethane elastomers with low modulus and hardness based on novel copolyether macrodiols

A series of copolyether macrodiols was prepared from either 1,10-decanediol or 1,6-hexanediol, by acid-catalyzed condensation polymerization using several comonomers to investigate the effect of copolymerization on reducing macrodiol crystallinity. The comonomers used to disrupt crystallinity included 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, and 1,7-heptanediol. The product copolyethers were identified as hydroxy terminated copoly(alkylene oxides) by ¹H- and ¹³C-NMR spectroscopy. Based on NMR results, the structures of the copolyethers were established as consisting of blocks of the principal monomer with comonomer 2,2-diethyl-1,3-propanediol incorporated to form only the end structural unit, whereas 1,4-cyclohexanedimethanol incorporated to form the end unit as well as part of the main chain. DSC results confirmed that the copolymerization produced macrodiols with lower crystallinity and lower T_g than those of the corresponding homopolyethers of the principal monomers, with two exceptions. The exceptions were 1,6-hexanediol/1,10-decanediol, and 1,10-decanediol/1,7-heptanediol copolyethers where no reduction in crystallinity was observed. A series of polyurethane elastomers with a constant hard segment percentage (40 wt %) was prepared using 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as the hard segment. Tensile test results and Shore hardness measurements demonstrated that copolyether macrodiols produced several polyurethanes with lower modulus and hardness than those of polyurethanes based on homopolyethers of the principal monomers. Of the comonomers studied, 2,2-diethyl-1,3-propanediol-based copolyether produced the polyurethane with the lowest hardness and modulus. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1373–1384, 1997