二氧化锰硫化剂对聚硫密封剂性能的影响

采用X射线衍射(XRD)法和扫描电镜(SEM)对不同晶型的二氧化锰(MnO2)进行了表征;然后将其配制成聚硫密封剂的硫化剂,考查了不同硫化剂对聚硫密封剂的力学性能、耐热性能和耐溶剂性能等影响。结果表明:γ-MnO2或β-MnO2硫化聚硫密封剂的耐热性能和耐水性能优于α-MnO2硫化聚硫密封剂;γ-MnO2硫化聚硫密封剂的性能相对最好,其经180℃热处理2 h后的拉伸强度增加了7.1%,在60℃水中浸泡7 d后的拉伸强度下降了39%;由不同晶型MnO2硫化的聚硫密封剂,其耐3#航空燃油性能相当;γ-MnO2最适合用作聚硫密封剂的硫化剂。     

环氧树脂硫化聚硫醚密封剂的性能研究

以液体聚硫醚橡胶作为密封剂的生胶、环氧树脂(EP)作为硫化剂,成功制备出一种综合性能良好的新型聚硫醚密封剂。结果表明:聚硫醚橡胶的热分解温度(296.4℃)高于聚硫橡胶(281.0℃),热循环后聚硫醚密封剂的拉伸强度变化率或断裂伸长率变化率(31%或42%)均低于聚硫密封剂(45%或64%),说明前者的耐高温性能优于后者;聚硫醚密封剂对多种基材表现出稳定的粘接性能,其常温剥离强度均超过7.5 kN/m(均为内聚破坏),并且其在60℃盐水/航空煤油双层液中浸泡7 d后仍为内聚破坏;聚硫醚密封剂受温湿度影响较小,其硫化速率较大,并且其硫化效果和加工性能良好。     

聚硫密封剂耐喷气燃料老化性能研究

聚硫橡胶是一种中温材料,其耐温等级(最高使用温度仅为120℃)已无法满足某些领域的使用要求。为此,以聚硫密封剂经3号喷气燃料150℃/24 h处理后的力学性能作为衡量指标,采用单因素试验法分别考察了不同类型的防老剂、硫化剂、填料和促进剂等对聚硫密封剂耐老化性能的影响。结果表明:在其他条件保持不变的前提下,当硫化剂为活性二氧化锰、补强填料为炭黑和防老剂为4020时,聚硫密封剂的耐老化性能相对最好;促进剂的类型对聚硫密封剂的耐老化性能基本无影响。     

聚硫橡胶对环氧树脂固化动力学及力学强度的影响

用红外光谱分析了在环氧树脂中加入聚硫橡胶的固化及增韧过程,通过差示扫描量热法研究了增韧体系的反应动力学,探讨了聚硫橡胶用量对固化产物力学强度的影响,并对试样断口形貌进行了扫描电镜观察。结果表明,聚硫橡胶的加入降低了环氧树脂的表观活化能而没有改变反应级数,使得固化反应的总放热量减少、放热过程更加平均。聚硫橡胶对环氧树脂的增韧效果明显,二者通过化学键结合,韧性撕裂的冲击断面形貌验证了这种活性增韧。当聚硫橡胶用量为30份(质量)时,环氧树脂固化物的冲击强度可达到未增韧者的896%。     

紫外光固化含硫密封剂的制备及性能

以聚硫代醚橡胶为基础胶,利用Thiol-ene点击反应制备了紫外光固化含硫密封剂。考察了光引发剂种类和用量以及烯烃种类、多元硫醇种类等对硫化后密封剂力学性能、热分解温度、玻璃化转变温度的影响。结果表明,相比于光引发剂184,光引发剂1173的固化效果更好,固化后的密封剂热稳定性更佳,且随着光引发剂用量的增加,密封剂的力学性能和热稳定性均下降,光引发剂1173的用量宜为0.03份（质量,下同）。采用三丙二醇二丙烯酸酯（TPGDA）作为固化剂固化的聚硫代醚密封剂力学性能较好,而且随着TPGDA用量的增加,密封剂的力学性能和热稳定性均上升,TPGDA的用量宜为1.00份。多官能度硫醇的加入可提高密封剂的交联度及玻璃化转变温度。     

Self-healable MnO2-cured polysulfide sealant and the effect of fillers on its self-healing ability

MnO₂-cured polysulfide sealants have been widely used in various industrial fields and the effects of MnO₂ and three fillers on their mechanical behavior, thermal property and self-healing ability were focused on in this paper. Under a moderate thermal stimulus, the tensile strength can be significantly restored due to the dynamic exchange of disulfide bonds in polysulfide segments. The residue of a small dosage of thiol promotes the healing process of polysulfide sealants. After healing at 75°C for 48 h, the tensile strength of 2 wt% MnO₂ cured sealant is restored to more than 90%. Then, this sealant is modified with three fillers to enhance the tensile strength, however, the addition of fillers hinder the healing process to some extent. Significantly, the sealant modified with 2.5 wt% TiO₂ can perform a certain enhancement without sacrificing the healing mechanical properties. These outcomes are helpful for the development of MnO₂-cured polysulfide sealants toward sustainable industrial applications.     

液态聚硫橡胶改性苯并噁嗪树脂的研究

为了提高苯并嗯嗪树脂的性能,使用液态聚硫橡胶对苯并嗯嗪树脂进行了改性研究。实验将不同配比的聚硫橡胶与苯并嚼嗪树脂进行共混并固化,利用傅立叶红外光谱（FTIR）、差示扫描量热法（DSC）、动态热机械分析仪（DMTA）分析了共混体系的结构、固化行为和玻璃化转变,测定了共混体系的热失重和冲击强度,分析比较了不同聚硫橡胶含量共混体系的结构、热性能和力学性能。结果表明改性苯并嗯嗪树脂的热性能和力学性能均得到不同程度的改善。得出如下结论：使用液态聚硫橡胶改性苯并嗯嗪树脂时,当聚硫橡胶加入量为5份（苯并嗯嗪树脂为100质量份）时,得到的改性树脂和纯嗯嗪树脂相比,韧性和热稳定性有显著提高,玻璃化转变温度也略有提高,复合材料的综合性能最好。     

航空聚硫密封剂人工热氧加速老化行为研究

对航空聚硫密封剂进行人工加速热氧老化试验,并采用光学显微镜、光泽度仪、邵氏A硬度计、万能试验机、动态力学分析(DMA)法和红外光谱(FT-IR)法等手段分析了热氧老化对聚硫密封剂的表面微观形貌、硬度、拉伸性能、耐热性和基团特征峰等影响。结果表明:随热氧老化时间延长,聚硫密封剂的光泽度逐渐降低,表面出现明显的泡孔缺陷;当老化时间为20~30 d时,密封剂的拉伸强度和断裂伸长率降幅明显;当老化时间为40 d时,聚硫密封剂的硫化反应更加完全,并且老化期间无可降解新官能团生成,而且其耐热性和室温储能模量基本不变,说明其耐热氧老化性能良好。     

偶联剂对改性聚硫密封剂粘接性能的影响

以改性液体聚硫橡胶为基胶,研究了硅烷偶联剂WD-50及螯合型钛酸酯偶联剂作为填料表面处理剂、直接加入密封剂体系、配制成粘接底胶及以上3种方式兼用对改性聚硫密封剂粘接性能的影响。结果表明,作为填料表面处理剂及直接添加到密封剂中都可以提高密封剂的剥离强度及内聚破坏率;配制成粘接底胶可以提高密封剂的内聚破坏率;采用WD-50作为轻质碳酸钙表面处理剂、同时在密封剂中加入一定量WD-50,并以WD-50和螯合型钛酸酯复合作为底胶可以使改性聚硫密封剂获得更理想的粘接性能。     

铅酸蓄电池用密封胶的配比对性能的影响

以改性环氧树脂(EP)与改性芳香胺固化剂为原料制备铅酸蓄电池极柱灌封用密封胶,着重研究了改性EP与固化剂的配比对胶粘剂性能的影响。实验结果表明,改性EP与固化剂配比对胶粘剂的初步固化时间、热变形温度、剪切强度和拉伸强度的影响显著;3种配比的胶粘剂耐酸碱性能均较好;当m(改性EP)∶m(固化剂)=100∶50时胶粘剂的综合性能最优,其初步固化时间为6 h、热变形温度为97℃、拉伸强度为72 MPa、剪切强度为3.56 MPa且对ABS的粘接达到材料破坏的程度。该胶粘剂室温固化具有一定的适用期,并具有良好的粘接性能、耐久性能和耐酸性能,可以满足蓄电池极柱灌封和粘接的技术要求。     

液体聚硫橡胶对聚硫密封剂性能的影响

以G系列液体聚硫橡胶为生胶、MnO2为密封剂的硫化剂,制备相应的聚硫密封剂。考察了生胶的不同相对分子质量(Mr)和交联度对相应密封剂性能的影响。结果表明:不同Mr或交联度的生胶均赋予相应密封剂良好的力学性能,特别是由低Mr的G44制成的密封剂具有相对更好的力学性能;密封剂的耐高温性能与生胶的Mr关系不大,主要受交联度影响较大;生胶的Mr越大或交联度越高,密封剂的耐水性越好,但Mr或交联度对密封剂的耐油性能(增重率<3%)和粘接性能影响较小。     

硫化剂原料及配方对聚硫密封剂硫化性能的影响

研究了聚硫密封剂硫化剂配方中不同原材料和用量对密封剂适用期、不粘期和标准硫化期的影响。结果表明,不同的二氧化锰和促进剂对密封剂性能的影响亦不同。随着促进剂用量的增加密封剂适用期、不粘期和标准硫化期均表现不同程度的降低。硫化抑制剂中硬脂酸和油酸效果相当,随着硬脂酸、油酸含量的增加,密封剂的不粘期和标准硫化期显著延长,需控制硫化抑制剂用量在合理范围内。     

Synthesis and characterization of diphenylsilanediol modified epoxy resin and curing agent

A series of diphenylsilanediol modified epoxy resins and novel curing agents were synthesized. The modified epoxy resins were cured with regular curing agent diethylenetriamine (DETA); the curing agents were applied to cure unmodified diglycidyl ether of bisphenol A epoxy resin (DGEBA). The heat resistance, mechanical property, and toughness of all the curing products were investigated. The results showed that the application of modified resin and newly synthesized curing agents leads to curing products with lower thermal decomposition rate and only slightly decreased glass transition temperature (T_g), as well as improved tensile modulus and tensile strength. In particular, products cured with newly synthesized curing agents showed higher corresponding temperature to the maximum thermal decomposition rate, comparing with products of DGEBA cured by DETA. Scanning electron microscopy micro images proved that a ductile fracture happened on the cross sections of curing products obtained from modified epoxy resins and newly synthesized curing agents, indicating an effective toughening effect of silicon–oxygen bond.     

微波技术在环氧树脂及其复合材料中的应用

论述了近年来微波固化技术在环氧树脂及其复合材料固化中的应用,重点比较了微波固化与传统热固化后环氧树脂及其复合材料的力学性能、热性能和粘结强度的变化,并对环氧树脂复合材料微波固化的研究进行了展望。     

硫化剂对聚硫代醚密封剂耐热性能的影响

分别以二氧化锰、环氧树脂、异氰酸酯为硫化剂制备聚硫代醚密封剂,通过不同条件下热空气老化后力学性能的变化和热失重分析,研究了硫化剂对聚硫代醚密封剂耐热性的影响。结果表明,用二氧化锰为硫化剂的聚硫代醚密封剂耐热性最好。     

Modification of polysulfide sealant with polysulfide polythio‐urethane‐urea

With a small amount of isocyanate‐terminated polysulfide (NCO‐PSF‐NCO) as additive, the commercial polysulfide‐based sealant had significant improvement in mechanical properties. The test results showed that 5% of NCO‐PSF‐NCO could help to rise 50% in the tensile strength and 27% in the ultimate elongation of the polysulfide sealant. The adhesive strength to substrates such as steel, epoxy‐coated or polyurethane‐coated surface also increased significantly. Dynamic mechanical thermal analysis and differential scanning calorimetry analysis revealed that formed polysulfide polythio‐urethane‐urea (polysulfide‐urea) contributed to a slight increase in the T_g of the polysulfide sealant. It might be due to the domains of polysulfide‐urea, which had effects of physical crosslinking and chain‐extending on the polysulfide sealant. However, the introduction of polysulfide‐urea structures had no appreciable influence on oil resistance of the polysulfide sealant. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Strengthening the mechanical properties of polysulfide adhesives by introducing polyurethane

Polysulfide adhesives are often subjected to breakage or even fracture caused by highly loaded vibrations and large deformations from the wing, limiting their practical use in aircraft fuel tanks. Inserting polyurethanes into liquid polysulfide systems is a viable approach to strengthening their mechanical properties and avoiding nonuniform dispersion of the curing agent. In this contribution, a series of sulfur-containing curing agents were prepared by liquid polysulfide and trimethylolpropane tris(3-mercapto propionate) (TMPMP) to minimize the effect of the polysulfide-urea (-NHCOS-) groups on water resistance. Subsequently, the two-component polysulfide adhesives were successfully synthesized via the prepolymerization method, and their chemical structure, mechanical properties, and solvent resistance were systematically evaluated. As expected, the large introduction of sulfur linkages and -NHCOS- groups provided excellent oil resistance and strong mechanical properties for polysulfide adhesives. Notably, Samples 2-4 exhibited the highest tensile strength of 1.11 ± 0.02 MPa, the greatest shear strength of 1.87 ± 0.04 MPa, and the best hardness of 81 ± 2 Shore A, with 122.0%, 523.3%, and 170.0% improvement over the control, respectively. Furthermore, the oil absorption rate of all samples was less than 3.0%, and their tensile strength remained almost unchanged after 30 days of immersion than before. We believe our paradigm can provide a valuable guideline for designing high-performance polysulfide adhesives.     

Effect of the structure of curing agents modified by epoxidized oleic esters on the toughness of cured epoxy resins

The aim of this study was to determine the effect of the ester carbon chain length of curing agents modified by epoxidized oleic esters on the toughness of cured epoxy resins. An amine‐terminated prepolymer (i.e., curing agent G) was synthesized from a bisphenol A type liquid epoxy resin and triethylene tetramine. The toughening curing agents (G1 and G2) were prepared by reactions of epoxidized oleic methyl ester and epoxidized oleic capryl ester, respectively, with curing agent G. Fourier transform infrared spectrometry was used to characterize the chemical structure of the curing agents. The effects of the carbon chain length of the oleic ester group in the curing agents on the toughness and other performances of the curing epoxy resins were investigated by analysis of the Izod impact strength, tensile strength, elongation at break, thermal properties, and morphology of the fracture surfaces of the samples. The results denote that the toughness of the cured epoxy resins increased with the introduction of oleic esters into the curing agents without a loss of mechanical properties and that the toughness and thermal stability of the materials increased with increasing ester carbon chain length. The toughness enhancement was attributed to the flexibility of the end carbon chains and ester carbon chains of the oleic esters in the toughening curing agents. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

改性聚硫密封胶的研制

以自制的改性聚硫液体橡胶为原胶,配以增塑剂、填充剂、触变剂制备了双纽分改性聚硫密封胶。研究表明,改性聚硫密封胶与混凝土的粘接性优于聚硫密封胶。讨论了聚硫橡胶含量对密封胶性能的影响,结果表明随着原胶含量的增加,密封胶的力学性能先增加后减小,当原胶质量分数为40％时,力学性能最优;讨论了密封胶A组分的贮存稳定性的影响因素,发现填料的pH值是影响A组分贮存稳定性的主要因素。     

The investigation on the curing process of polysulfide sealant by in situ dielectric analysis

In this work, in situ dielectric analysis (DEA) was employed for the first time to the best of our knowledge, to monitor the curing process of polysulfide (PSF) sealant using manganese dioxide (MnO₂) as the curing agent, where the gel point and ending point were determined. The obtained results were verified by rheological tests of dynamic mechanical analysis and tensile strength tests. It showed a significant difference between this curing process and those of usual thermosetting materials. The influences of the pH value of the samples and curing temperature were investigated and discussed in detail. Also, activation energies of the curing reaction of the samples with different pH values were calculated. The results proved DEA as a reliable and useful method for in situ monitoring PSF–MnO₂ curing process. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012