异氰脲酸酯基团对聚氨酯弹性体性能影响研究

引入异氰脲酸酯基团可提高聚氨酯弹性体的耐热性能,但同时对其他性能有一定影响。通过改变NCO含量考察异氰脲酸酯基团对聚氨酯弹性体的力学性能及耐溶剂性能的影响。力学性能测试结果表明,其硬度、拉伸强度和撕裂强度均在NCO质量分数为8％时达到极大值,分别为邵A60、10．33MPa和48．84kN／m,扯断伸长率随NCO含量增加单调减小,100％定伸强度单侧增大;耐溶剂实验表明,聚氨酯弹性体在NCO质最分数为8％时耐溶剂性能最好。     

不同异氰酸酯型聚氨酯弹性体的制备与力学性能研究

采用不同结构的异氰酸酯和多元醇制备了一系列聚氨酯弹性体,主要考察了异氰酸酯种类对聚氨酯弹性体力学性能的影响.研究表明,由1,5-萘二异氰酸酯制得的弹性体拉伸强度和撕裂强度较高,分别为38.75MPa和109.77 kN/m,而由对苯二异氰酸酯制得的弹性体具有最大的扯断伸长率(557.84％).此外还研究了多元醇种类和扩链系数α对弹性体力学性能的影响,研究表明,选用聚ε-己内酯二醇制得的弹性体具有较好的性能,且拉伸强度和撕裂强度均随扩链系数的增大先增大后减小,而扯断伸长率一直增大.     

PTMG／TDI型聚氨酯弹性体的制备及力学性能研究

以聚四氢呋喃醚二醇（PTMG）、2,4-甲苯二异氰酸酯（TDI）、3,3’-二氯-4,4’-二胺基二苯甲烷（MOCA）或3,5-二甲硫基甲苯二胺（E-300）为主要原料,采用预聚体法合成浇注型聚氨酯弹性体（PUE）。分析了预聚体NCO基含量、PTMG软段相对分子质量、两种扩链剂以及扩链系数对PUE力学性能的影响。结果表明,随着预聚体NCO基含量增加,PUE的硬度、拉伸强度、300％定伸应力和撕裂强度提高,扯断伸长率下降,扯断永久形变发生微小变化;随着软段相对分子质量的不断提高,PUE的硬度、拉伸强度、300％定伸应力和撕裂强度缓慢下降,而扯断伸长率和扯断永久形变升高;在其它条件相同时,扩链剂E-300与MOCA相比,综合力学性能较好。     

Morphology and mechanical properties of rubber modified aromatic-ether bismaleimide matrix resins

An aromatic ether bismaleimide (BMI) was modified by copolymerization with various CTBN and ATBN liquid elastomers. Dynamic mechanical (DMA), flexural, and SEM fractography studies indicate that cured specimens containing various amounts of the different elastomers have widely varying morphologies and properties. The experimental parameters of interest in this study included the type of elastomer reactive end group, elastomer acrylonitrile content, elastomer concentration, and cure reaction conditions. The ATBNs are clearly more compatible than CTBNs. CTBN modified compositions show a distinct, low temperature rubber phase mechanical loss dispersion, reduced modulus and ultimate strength values, and only slight improvements in elongation. Cured compositions with small amounts of ATBN elastomers (5 phr), however, show no reduction in modulus but improved elongation and ultimate strength values. The “rubber” domains in these systems are small, typically < 5 μm, and consist of copolymerized BMI and elastomer. DMA data for these systems show no distinct low temperature elastomer peak but a broad “interphase” loss dispersion covering a wide range of temperatures. Failure in the ATBN modified BMIs involves initiation of numerous microcracks with obvious crack deflection at the rubber particles. No cavitation of rubber particles occurs, as is frequently the case with the CTBNs.     

Correlation between microstructure and physical properties in styrene–ethylene copolymers

The structural organization and the physical properties of a new copolymer styrene–ethylene have been analyzed. The composition was 80% of ethylene units, corresponding to 52% in weight, with a distribution of styrene units in the chain implying the absence of styrene–styrene sequences. The length of the polyethylene chains, limited by the insertion of the phenyl group, is not sufficient to allow good crystallization, and in fact the copolymer shows a very low crystailinity, of the order of 5–10%, and a broad melting range, with a peak centered at 120°C. The small crystalline domains are segregated into an amorphous matrix, producing a thermoplastic elastomer. The mechanical properties at large deformation were analyzed at different temperatures. The copolymer shows good elastic properties, in terms of deformation reversibility as well as of energy dissipation in the hysteresis cycles. Also the stress level and the elastic recovery are very good, if compared with others thermoplastic elastomers. © 1995 John Wiley & Sons, Inc.     

氟橡胶的并用改性研究进展

氟橡胶的特殊性能是由其分子中固有的氟原子结构特点所决定的,但氟橡胶也存在不足之处,如弹性差、撕裂强度低、耐低温性能欠佳、易压缩变形、生胶加工性能差等。为了提高氟橡胶及其制品的性能,国内外学者对氟橡胶进行了大量的改性研究工作,包括主链改性、并用改性、填充改性和表面改性等,其中并用改性具有工艺简单、成本低廉、易于推广等优点,是开发高分子材料新品种的重要途径。本文详细综述了目前氟橡胶并用改性的研究状况。     

Urethane polymers from hydroxylated fish oil

Alewife fish oil was hydroxylated by performic, peracetic and pertungstic acid methods. Products were compared with respect to yield, free acid, hydroxyl number, saponification value and peroxide value. Fish oils oxidized with performic acid resulted in high yields (83% to 95%), low acid values (0.12 to 0.19), high hydroxy (142 to 245) and saponification (247 to 271) numbers, and relatively low peroxide values (72 to 266). Performic acid hydroxylated alewife and menhaden oils were used to prepare urethane foams. These foams exhibited characteristic low compressive strengths at 10% deflection (6.4 to 9.5 psi), low density (1.45 to 1.65 pcf), high porosity (0.7 to 1.7% closed cells) and high water absorption compared to a conventional polyether urethane foam. Performic acid hydroxylated alewife oil was further refined, using cation and anion exchange resins, for use in the preparation of urethane elastomers. These polymers generally exhibited higher tensile and Graves tear strengths than a comparable castor oil elastomer used as a control. though dielectric strengths were similar for both fish oil and castor oil elastomers, tensile elongation at break point was greater for the castor oil elastomers. When the isocyanate index of the fish oil elastomers was increased from 105 to 156, the Graves tear strength exhibited the greatest change.     

PDA型PUR弹性体的制备与性能

以聚己二酸二乙二醇酯二醇(PDA)为软段,4,4′–二苯基甲烷二异氰酸酯(MDI)和1,4–丁二醇(BDO)为硬段,采用预聚体法制备一系列PDA型PUR弹性体。采用力学性能测试、广角X射线衍射(WAXD)、傅立叶变换红外光谱(FTIR)、差示扫描量热(DSC)、热重(TG)分析和维卡软化点温度测定等研究手段,研究硬段含量对其力学性能、微观形态和热性能的影响。结果表明,随着硬段含量的增加,PDA型PUR弹性体的硬度、拉伸强度、300%定伸应力、拉伸永久变形和撕裂强度都增大,当硬段含量为40.1%时,弹性体的综合力学性能最佳,硬度(邵A)为88,拉伸强度为33.9 MPa,300%定伸应力为12.5 MPa,拉伸永久变形为31%,撕裂强度为90.3 k N/m;WAXD分析表明,弹性体为无定型结构;FTIR分析表明,硬段含量的增加使弹性体总的氢键化程度增加,微相分离程度改善;DSC测试表明,硬段含量的增加使弹性体的微相分离程度提高;TG和维卡软化点温度测试表明,弹性体的热性能随着硬段含量的增加而提高,当硬段含量为40.1%时,弹性体的初始分解温度(失重5%的温度)和维卡软化点温度分别达到324.5℃和144.1℃,具有较好的热性能。     

Fracture energies and tensile strength of an EPDM/PP thermoplastic elastomer

Measurements of the tear strength of EPDM/PP thermoplastic elastomers (EPDM/PP TPEs, Santoprene 201‐87) were carried out at various rates and temperatures. In addition, a cutting technique developed recently was adopted to measure the fracture energy in a process where a well‐controlled geometry of the crack tip was obtained. Results show that the EPDM/PP TPEs possess a relatively high tear strength of 10.40 ± 0.94 kJ/m² at room temperature. Furthermore, good tear strength is still preserved, about 1.87 ± 0.38 kJ/m², at 150°C, where some PP crystals are melted and start to flow. In contrast, the intrinsic strength of EPDM/PP TPEs determined from a cutting test is varied slightly, 700–1000 J/m², over a wide range of temperatures and rates. A comparison of the fracture energy measured by tearing and cutting tests is provided and discussed. The energy density per unit volume of EPDM/PP TPEs determined from the cutting test is 9.7 GJ/m³, which is about twice larger than that for the rupture of C C bonds at room temperature. It is suggested that plastic yielding is a more effective process to enhance the toughness than is simply viscoelastic motion. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1033–1044, 2000     

Adhesion of elastomers: Dwell time effects

The strength of adhesion of elastomers to rigid substrates generally increases with time of contact. This effect has been studied for samples of butyl and chlorobutyl rubber adhering to some rigid substrates. The peel strength increased continuously over long periods of contact until in some cases failure became cohesive within the elastomer layer. At higher temperatures the strength increased more rapidly, consistent with the WLF relation governing molecular motions. It is postulated that slow molecular rearrangements occur at the interface and increase the bond strength. A criterion for the observed transition from interfacial to cohesive failure is suggested.     

ADHESION OF ELASTOMERS: DWELL TIME EFFECTS

The strength of adhesion of elastomers to rigid substrates generally increases with time of contact. This effect has been studied for samples of butyl and chlorobutyl rubber adhering to some rigid substrates. The peel strength increased continuously over long periods of contact until in some cases failure became cohesive within the elastomer layer. At higher temperatures the strength increased more rapidly, consistent with the WLF relation governing molecular motions. It is postulated that slow molecular rearrangements occur at the interface and increase the bond strength. A criterion for the observed transition from interfacial to cohesive failure is suggested.     

高性能有机氟材料制备科学及应用进展

有机氟材料具有优异的热氧稳定性、耐化学腐蚀性、耐老化性、不黏性、电绝缘性以及极小的摩擦系数等特性,因此作为一种不可替代的材料广泛应用于高新技术产业。近年来高新技术产业发展对高性能有机氟材料的需求引发了学术界和工业界对氟材料的研究兴趣。依据本文作者的研究经历及有机氟材料的发展方向,本文介绍了氟树脂（新型含氟聚合物、电活性含氟聚合物、新型全氟磺酸聚合物、聚四氟乙烯3D打印）及氟橡胶（过氧化物硫化氟橡胶、耐低温氟醚橡胶、耐高温全氟醚橡胶、全氟聚醚基类玻璃橡胶）的制备科学及应用进展,特别阐述为了满足航空航天、能源、信息等高新技术产业需求发展的新一代高性能有机氟材料。本文也介绍了近期出现的聚四氟乙烯新成型技术及类玻璃氟橡胶。文章指出发展绿色环保和高效的高性能有机氟材料制备及成型加工方法是今后的发展方向。     

Synthesis,characterization and properties of biocompatible poly(glycerol sebacate) pre‐polymer and gel

Poly(glycerol sebacate) (PGS) is an elastomer with potential biomedical applications but it suffers from problems with irreproducible synthesis and the unacceptable toxicity of very soft PGS elastomers. To establish the reason for these problems, PGS was synthesized using different temperatures and reaction times, and the reaction was monitored by titration of the unreacted carboxylic groups and measurement of the mass loss during synthesis. It was found that evaporation of glycerol was a major cause of irreproducibility of the elastomer synthesis and this was more significant at higher reaction temperatures. The polymer microstructure was analysed using NMR spectroscopy and all twelve acylglyceride ¹³C‐signals as well as two small extra peaks of the residual glycerol were observed for the pre‐polymer. For the PGS gel, the glyceride moieties were characterized using NMR spectroscopy for the first time. The modulus and ultimate tensile strength of the gel increased with longer cure times and at higher cure temperatures while the elongation to break decreased and this was interpreted in terms of network theory. The cell viability of mouse fibroblasts was better for PGS samples with a higher conversion.© 2012 Society of Chemical Industry     

Stabilization of filled polysiloxane elastomers to cyclic stress at elevated temperature through use of zinc oxide fillers

The susceptibility of filled polysiloxane elastomers to cyclic stress at elevated temperatures is investigated. It is shown that zinc oxide fillers, unlike other fillers examined previously, can produce filled elastomers with remarkable stability to combined mechanical and thermal stresses. The influences of filler concentration, diphenylsiloxane incorporation, and molecular weight between network crosslinks are examined. The data demonstrate that the elastomer stability to cyclic stress at elevated temperature increases with increasing filler content and does not correlate with diphenylsiloxane content. It is suggested that chemical interactions between the polysiloxane network and the filler surfaces control the response to cyclic stress at elevated temperature and that the response strongly depends on the type of filler selected. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1499–1509, 1997     

高剪切应力下不同弹性体对ABS材料力学性能影响

采用材料在熔融挤出共混过程中提高双螺杆挤出机螺杆转速的方法,研究了较高螺杆转速条件下双螺杆挤出机的高剪切应力、不同弹性体(SEBS、POE、EVA、NBR)等对ABS材料力学性能的影响.结果表明:双螺杆挤出机的高剪切应力可促进弹性体颗粒的分散和界面结合力的增强,引起共混材料力学性能的改善;NBR、EVA等弹性体有利于ABS材料韧性的提高,POE、EVA等弹性体有利于ABS材料加工流动性的改善.在220℃的挤出温度下,当螺杆转速由240 r/min提高至1200 r/min时,其中ABS/NBR(质量比90/10)共混材料的缺口冲击强度由22.1 kJ/m2提高至28.8 kJ/m2,提高了30%,比纯ABS树脂提高一倍.     

Poly(fluoroalkoxyphosphazenes)—versatile seal materials

Poly(fluoroalkoxyphosphazene) fluoroelastomers are members of a new family of polymers based on a phosphorous–nitrogen backbone. Physical property evaluation tests have demonstrated that these fluorelastomers possess excellent stress–strain properties, low-temperature flexibility, thermal stability, and resistance to a variety of demanding environments including synthetic lubricants, hydrocarbon fuels, and aqueous caustics. Their service temperature range is about ?60° ?200°C. Poly(fluoroalkoxyphosphazene) fluoroelastomers have shown the capability to function in severe dynamic applications; i.e., lip seals (1? in. I.D.) performed for >1000 hr at 5500 rpm in MIL L-7808G lubricant at 115°C. Also, O-ring seals successfully completed a 1000-hr dynamic qualification test over a temperature range of ?54°–163°C in a rod seal test apparatus. These elastomers can be used for seals, O-rings, gaskets, diaphragms, hose, and protective coatings.     

挤出反应温度与剪切应力对动态硫化PP/EPDM性能的影响

采用动态硫化的方法,在双螺杆挤出机中制备了聚丙烯(PP)/三元乙丙橡胶(EPDM)热塑性弹性体,研究了挤出反应温度与螺杆转速提供的剪切应力对动态硫化PP/EPDM热塑性弹性体性能的影响。结果表明,适当提高挤出反应温度或螺杆转速可提高PP/EPDM热塑性弹性体的拉伸强度、拉断伸长率和凝胶含量,当挤出反应温度为200℃、螺杆转速为600 r/min时,热塑性弹性体的综合拉伸性能最好,拉伸强度为19.87 MPa,拉断伸长率为527.3%,凝胶含量为54.69%。高螺杆转速提供的高剪切应力可在一定程度上提高PP/EPDM热塑性弹性体的熔融温度。     

PVC/CM热塑性弹性体的开发研究

研究了氯化聚乙烯橡胶(CM)的牌号及用量、增塑剂用量对PVC/CM热塑性弹性体性能的影响.试验结果表明:①PVC与CM5236用量比为100∶10、DOP用量为80份时,PVC/CM热塑性弹性体的力学性能最佳,拉伸强度可以达到12 MPa,断裂伸长率可达到400%~500%,而硬度则保持在65(邵氏A)左右;②高聚合度...     

MDI浇注型聚氨酯弹性体的加工特性

介绍了MDI浇注型聚氨酯弹性体(MDI-CPUE)的聚合反应特点和3种加工方法的特点及物性.讨论了预聚物法硬段含量对MDI-CPUE物性的影响,随着体系中硬段含量的增加,MDICPUE的硬度、模量、撕裂强度、拉伸强度依次提高,伸长率和回弹降低.     

Electrical breakdown of an acrylic dielectric elastomer: effects of hemispherical probing electrode’s size and force

Dielectric elastomers are widely investigated as soft electromechanically active polymers (EAPs) for actuators, stretch/force sensors, and mechanical energy harvesters to generate electricity. Although the performance of such devices is limited by the dielectric strength of the constitutive material, the electrical breakdown of soft elastomers for electromechanical transduction is still scarcely studied. Here, we describe a custom-made setup to measure electrical breakdown of soft EAPs, and we present data for a widely studied acrylic elastomer (VHB 4905 from 3M). The elastomer was electrically stimulated via a planar and a hemispherical metal electrode. The breakdown was characterized under different conditions to investigate the effects of the radius of curvature and applied force of the hemispherical electrode. With a given radius of curvature, the breakdown field increased by about 50% for a nearly 10-fold increase of the applied mechanical stress, while with a given mechanical stress the breakdown field increased by about 20% for an approximately twofold increase of the radius of curvature. These results indicate that the breakdown field is highly dependent on the boundary conditions, suggesting the need for reporting breakdown data always in close association with the measurement conditions. These findings might help future investigations in elucidating the ultimate breakdown mechanism/s of soft elastomers.