Relationships of tensile strength with crosslink density for the high-carbon black-filled EPDM compounds with various softeners

Equilibrium swelling and rheological tests were adopted to systematically investigate the effects of softener type and dosage on the crosslink densities. The results turned out that the chemical crosslink density could be distinguished from the physical crosslink density by comparing the results of equilibrium swelling and rheological tests. The liquid butadiene (LB) as a softener leads to the greatest reduction in crosslink density, followed by polyethylene wax (PW) and paraffinic oil (PO). The tensile strength decreases with increasing PO content while shows peak values with increase of LB and PW contents. The dependencies of chemical crosslink density on the aging time under 150°C are quite different for the three softeners, which can be expected from the double crosslinking networks consisting of small softener and large main crosslinking networks. Further investigation has been performed to correlate the tensile strength with chemical crosslink density of ethylene propylene diene monomer elastomer vulcanizates. Three different linear relationships can be obtained for the softeners independent of the aging time. It can now be expected from this study that the role of some new softeners in rubber compounds is not only confined to plasticization but also forms crosslinking networks in the peroxide-cured rubbers.     

SBS Thermoplastic Elastomer Based on Dynamic Metal-Ligand Bond: Structure,Mechanical Properties,and Shape Memory Behavior

A Cooper(II) (Cu²⁺)-nitrogen coordination-crosslinked network is designed in poly(styrene-co-butadiene-co-styrene) (SBS) to change commercial elastomers into advanced soft materials. Herein, ligand groups into SBS molecular chains by the 3,6-di(2-pyridyl)-1,2,4,5-tetrazine (DPT) click reaction are first introduced. The results from fourier transform infrared (FT-IR), 1H-nuclear magnetic resonance, and X-ray photoelectron spectroscopy (XPS) are verified the successful modification of SBS. The DPT-grafted SBS could then coordinate with copper sulfate (CuSO₄) to form a Cu²⁺-nitrogen bond, which is further characterized using FT-IR, XPS, atomic force microscope, scanning electron microscope, and geometric structure calculations. After modifying SBS to form an SBS-DPT/CuSO₄ composite (SBS-DPT2-Cu10), the tensile stress is improved from 11.43 to 23.25 MPa, while the elongation at break is remained almost unchanged, and the corresponding toughness is increased from 33.21 to 63.26 MJ m^–3. Moreover, the dynamic nature of the Cu²⁺-nitrogen coordination bonds enables the SBS-DPT/CuSO₄ composite to exhibit sustained thermoplastic performance and excellent shape memory behavior under an external thermal stimulus.     

氧化壳聚糖改性抗菌蚕丝织物的制备及其性能

为获得持久抗菌的功能丝绸材料,采用硝酸、磷酸、亚硝酸钠体系将原料壳聚糖的C6位伯羟基选择性氧化为羧基制得水溶性氧化壳聚糖(OCS),使OCS的羧基与脱胶蚕丝织物(SFF)的氨基反应,得到氧化壳聚糖改性蚕丝织物(OCSMSF)。借助核磁共振仪、扫描电子显微镜、红外光谱仪、X射线衍射仪等手段表征了OCS与OCSMSF的化学结构,测试了OCSMSF的力学、吸湿、抗菌等性能。结果表明:酰胺反应已将氧化壳聚糖分子化学键合在SFF中,OCS改性蚕丝纤维的结晶度降低;在优化反应参数条件下,OCS接枝蚕丝织物的质量增加率达到9.17%,OCSMSF的强力略有减小,而吸湿性提高42.92%,OCSMSF对测试细菌的抑菌率大于94%,且抗菌耐洗涤性好,同时OCSMSF对仙人掌黄酮提取物有良好的缓释效果。     

Synthesis and properties of polyurethane elastomers based on renewable castor oil polyols

In this contribution, castor oil polyols with functionality of f = 2.7 and f = 2 are used as soft segments (SS) for synthesizing polyurethane elastomers (PUEs) without addition of petroleum-based polyol. The effect of molar ratio of castor oil polyols on structure and properties of PUEs has been investigated by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, X-ray diffraction, tensile, swelling, and water absorption tests. The results reveal that hydrogen bonding mainly exists in hard segments (HSs) and weakens with decreasing the molar percentage of castor oil polyol (f = 2.7) in SS. T _g of SS decreases while T _g of HS remains constant as molar percentage of castor oil polyol (f = 2.7) decreased. The initial degradation temperatures (T_5%) are above 300 °C and independent of the molar ratio of castor oil polyols. However, the temperature at 50% weight loss (T_50%) decreases significantly as molar percentage of castor oil polyol (f = 2.7) decreased. Moreover, PUEs exhibit very low water absorption rate, <1%, after immersing in water for 140 h at room temperature. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47309.     

A triple-shape memory material fabricated by in situ crosslinking of poly(butylene adipate-co-terephthalate)/ε-polycaprolactone via electron-beam irradiation and its triple-shape memory effects

In this work, we fabricated a triple-shape memory polymeric material though in situ crosslinking of poly(butylene adipate-co-terephthalate)/ε-polycaprolactone blends induced by electron beam irradiation. The intrinsic property of irradiation crosslinking, crosslinking rule in this heterogeneous system, formation of interfacial bridge molecular, and the resulted interfacial strength were investigated. No obvious interfacial slips were observed in tensile test, and the elongation at break was above 900%. The high-temperature relaxation and recovery experiments at nonlinear region confirmed the excellent hyperelasticity and recovery ratios (R_r ) can be as high as 95% for samples irradiated above 96 kGy. The mismatch between heating rate and relaxation kinetics resulted in both instable temporary shapes and heating-mode dependent recovery behavior during the recovery process. Self-stability of the temporary shape at middle temperature was also emphasized in view of the phenomenon that the second R_r was above 100% in our experiments. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48588.     

配方因素对氟橡胶高温撕裂性能的影响

研究了硫化剂品种、双酚AF用量、促进剂BPP用量、补强剂品种及炭黑N990用量对不同测试温度下氟橡胶撕裂强度的影响,采用核磁共振法测定了不同温度下氟橡胶硫化胶的交联密度,研究了氟橡胶的高温撕裂强度与其交联密度间的关系。结果表明,随着测试温度的增加(25℃增加到200℃),不同配方的氟橡胶的撕裂强度均明显降低。在100~200℃温度范围内,双酚AF/BPP硫化的氟橡胶的撕裂强度高于过氧化物或胺类硫化氟橡胶的撕裂强度。随着双酚AF用量的增大,氟橡胶的常温撕裂强度明显降低,而高温撕裂强度略有下降。促进剂BPP用量增大,氟橡胶的常温和高温撕裂强度均变化不大。几种补强剂中,沉淀法白炭黑补强氟橡胶在200℃时的撕裂强度仅为25℃时撕裂强度的0.6%。测试温度从25℃升至200℃,炭黑N990补强氟橡胶的撕裂强度降低幅度较小,随着N990用量的增大,氟橡胶的常温撕裂强度增幅明显,而高温撕裂强度略有提高。测试温度升高,氟橡胶硫化胶的交联密度减小,同时撕裂强度也降低,双酚硫化时,在相同测试温度下,氟橡胶的交联密度越小,撕裂强度越大。     

热交联处理对聚苯硫醚结晶行为的影响

采用热台偏光显微镜和差示扫描量热法,研究了直链型低分子量聚苯硫醚(PPS)热交联处理后的等温结晶行为,考察了热处理时间对PPS球晶生长速率与晶体形态的影响.结果表明:球晶的生长速率随热交联时间的延长呈先升高后降低的趋势,20min时结晶速率达到最大值;经过一定时间的热交联处理后,PPS的晶体形态更趋完善.当热交联时间超过60min后,球晶超结构基本消失.     

Steady shear and viscoelastic properties of a micro‐crosslinked acrylamide‐based terpolymer

A water‐soluble micro‐crosslinked associating polymer (PASA‐PL): poly (acrylamide/butyl styrene/sodium 2‐acrylamido‐2‐methylpropane sulphonate) (PASA)–phenolic aldehyde (PL) was prepared to reduce the critical associated concentration and enhance the thickening properties for the linear PASA polymer in aqueous and brine solutions. The consecutive steady shear and viscoelastic properties were investigated to explore the correlations between the rheologic performance and supramolecular structures for the PASA‐PL brine solutions. Upon consecutive steady shear, the intermolecular hydrophobic association is greatly reinforced because of the expansion of the coiled PASA‐PL chains at the suitable shear rate, and the brine solution exhibits obvious shear thickening behavior. The steady shear results show that the intermolecular hydrophobic association is reversible, and that the polymer chains do not degrade upon shearing. The PASA‐PL brine solutions with 50 g L⁻¹ NaCl have predominantly elastic character over the angular frequency range at the polymer concentration higher than 1.0 g L⁻¹, which is remarkably strengthened with a slight increase in polymer concentration. The PASA‐PL brine solutions display a salt‐thickening effect and predominantly exhibit elastic character over the angular frequency range at 10–50 g L⁻¹ NaCl. These results demonstrate that the viscoelastic behavior of the PASA‐PL solutions mainly depends on the formation of hydrophobically associated structures via the intermolecular association strengthened by the micro‐crosslink of PASA with PL. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚丙烯防腐夹克料的制备研究

采用交联复合共混技术通过双螺杆反应挤出共混制备了聚丙烯防腐涂层夹克料,考察了螺纹捏合组合强度、螺杆转速及交联剂用量对产品力学性能的影响。结果表明,在12组螺纹捏合组合的条件下,螺杆转速为130 r/min,交联剂用量为0.10 %时制备的聚丙烯夹防腐夹克料力学性能较好,其维卡软化点达到146 ℃,缺口冲击强度常温达到91.5 kJ/m2,特别是0 ℃下的低温冲击性能达到15.2 kJ/m2,熔体流动速率在0.9～1.1 g/10 min之间。     

NBR/OMMT纳米复合材料的性能研究

通过机械共混法制备了丁腈橡胶/有机蒙脱土（NBR/OMMT）纳米复合材料。利用X射线衍射（XRD）、透射电镜（TEM）对复合材料的结构进行表征。研究了OMMT用量对复合材料硫化性能、交联密度的影响。结果表明,少量的OMMT（5份）缩短了正硫化时间（t90）,提高了交联密度。随着OMMT用量的增加（5～20份）,t90逐渐延长,交联密度逐渐减小。对照炭黑的增强机理,对OMMT对橡胶的增强机理进行了初步探讨。从力学性能的变化趋势可以看出,随着OMMT用量的增加,拉伸强度提高。由此可知,OMMT对橡胶的增强机理是OMMT片层对橡胶大分子链的吸附作用。同时还研究了复合材料的热空气老化性能和热稳定性能。