螯合配位型硼酸酯偶联剂的制备及应用研究

报道了螯合配位型硼酸酯偶联剂的合成工艺、结构特点、性能指标、降粘特性、对改性碳酸钙白度与吸水率影响，以及对PVC／CaCO3复合体系拉伸强度、冲击强度、断裂伸长率的影响。研究表明，合成的硼酸酯偶联剂具有较好的降粘特性和增强、增填作用，是一类新型的偶联剂。     

偶联剂在环氧树脂／纳米SiO2复合材料中的应用

采用偶联剂、通过原位分散聚合法制得了环氧树脂／纳米二氧化硅（ｎａｎｏ－ＳｉＯ２）复合材料。探讨了偶联剂的用量对复合材料性能的影响,利用拉伸试验、冲击试验、扫描电镜、热失重分析等方法研究了加与不加偶联剂的复合材料的结构和性能。结果表明：在偶联剂的作用下,ｎａｎｏ－ＳｉＯ２较均匀地分散在环氧树脂基体中,有效地增加了环氧树脂的强度及韧性,并提高了环氧树脂的耐热性。     

钛酸酯偶联剂对抗菌沸石/聚丙烯共混体系的影响

采用钛酸酯偶联剂对抗菌沸石进行表面修饰,然后将其与聚丙烯共混造粒并纺丝。对共混切片进行DSC、扫描电镜以及纤维拉伸强度测试。结果表明:钛酸酯偶联剂的加入能完善共混体系的结晶,提高结晶度,促进抗菌沸石的分散以及减缓共混纤维拉伸强度的下降,其影响程度与钛酸酯含量有关。同时,抗菌沸石含量也是影响共混体系结晶、分散性及纤维拉伸强度的主要因素。     

助剂对氢氧化铝和碳酸镁复配阻燃LLDPE性能的影响

将协效剂白炭黑、硼酸锌、低熔点玻璃和硅烷偶联剂、铝酸酯偶联剂分别添加到碳酸镁/氢氧化铝复配阻燃的线型低密度聚乙(烯LLDPE体)系中,考察了这些助剂对体系阻燃性能和力学性能的影响。结果表明:几种助剂对体系的氧指数影响较小;白炭黑可以明显提高体系的拉伸强度,硼酸锌对体系的断裂伸长率影响最小;对拉伸强度而言使,用铝酸酯偶联剂优于硅烷偶联剂。     

酚醛环氧／双酚A二（二苯基）磷酸酯／有机蒙脱土阻燃ABS Ⅱ．偶联剂和硼酸锌对阻燃ABS性能的影响

将硼酸锌和偶联剂添加到以酚醛环氧树脂（NE）／有机蒙脱土（OMMT）纳米复合物与双酚A二（二苯基）磷酸酯（BDP）阻燃ABS体系中制备了无卤阻燃ABS。研究发现添加偶联剂KH560的阻燃ABS的氧指数和冲击强度都比添加KH550的高。KH560质量分数为0．5％时对阻燃体系有一定的协同效应，提高了体系的氧指数。硼酸锌在一定范围内对NE／OMMT-BDP阻燃ABS体系也有协同效应，随着其用量增加，氧指数先增大后减少；增加硼酸锌用量使冲击强度明显下降，而拉伸强度则是先升后降，在其质量分数为3％时，拉伸强度达到最高。     

钛酸酯偶联剂对填充聚烯烃的机械性能和流变性的影响

本实验研究了钛酸酯偶联剂对微粒填充的聚烯烃熔融物流变性的影响。无机填料用碳酸钙、滑石粉和玻璃纤维;聚烯烃用高密度聚乙烯(HDPE)和聚丙烯(PP)。发现偶联剂(Kenrich石油化学厂的TTS和EDTS—201)使填充聚烯烃的熔融粘度明显降低。而使用不同的无机填充物和偶联剂,对注射模塑制品的机械性能的影响依次进行了研究。发现添加钛酸酯偶联剂的结果,使模量和拉伸强度降低,而填充体系的流变性和抗冲击强度增加。发现PP—CaCO_3—TTS和HDPE—EDTS 201体系随着钛酸酯偶联剂的增加,冲击强度的改善接近100％。PP—CaCO_3—TTS制品的极限拉伸伸长率接近纯PP。     

碳纤维及偶联剂用量对环氧树脂性能的影响

采用浇注成型工艺制备了碳纤维增强热固性树脂基复合材料;研究了常用的不同偶联剂(硅烷偶联剂及钛酸酯偶联剂)对环氧树脂增强增韧作用的差别;集中考察了偶联剂用量、碳纤维用量对环氧树脂力学性能的影响。研究结果表明,硅烷偶联剂的效果好于钛酸酯偶联剂;碳纤维可明显改善体系的力学性能,各强度随纤维含量的增加而增大,当纤维含量超过一定量时,力学性能开始下降,在纤维添加量为基体树脂的5 wt%左右时,所得体系的综合性能较好。     

Mg(OH)2表面处理对LDPE力学性能及加工性的影响

选择了多种偶联剂对氢氧化镁（MH）进行表面处理；研究了表面处理对LDPE／MH体系的力学、加工和分散性能的影响。结果表明，偶联剂能显著提高材料的断裂伸长率，但会略微降低其拉伸强度。硅烷、钛酸酯偶联剂的最佳使用量在1％～2％；而脂肪酸处理剂的最佳使用量在4％～6％。偶联剂的选择影响到材料的力学性能，脂肪酸ste—zn，硅烷偶联剂中Al51，钛酸酯偶联剂JN201有较好的处理效果。表面处理体系有较好的流动性和加工性能。SEM观察表明，未经表面处理体系的粒子分散性比经表面处理体系的粒子分散性要差。     

环氧树脂／纳米蒙脱土胶粘剂耐蚀及耐磨性研究

通过正交试验研究了环氧树脂、固化剂、增韧剂、有机化纳米蒙脱土、偶联剂对环氧胶粘剂拉伸剪切强度的影响,并对所得配方的胶粘剂进行腐蚀和冲蚀磨损试验,由此推荐环氧树脂／纳米蒙脱土胶粘剂各组分的最佳加入量。     

环氧树脂/有机蒙脱土复合材料的制备与力学性能研究

利用插层聚合法制备了环氧树脂/有机蒙脱土(EP/OMMT)复合材料.采用XRD对复合材料进行了表征,并研究了复合材料力学性能.实验表明:环氧树脂/有机蒙脱土形成了剥离型的纳米复合材料结构;环氧树脂中加入适量的有机蒙脱土,可以提高环氧树脂的拉伸强度和冲击强度.当经过改性的OMMT质量分数为5%时,EP/钛酸酯偶联剂(Coupler)-OMMT复合材料的拉伸强度达到51.21 MPa,提高了40.26%;当OMMT质量分数为3%时,EP/Coupler-OMMT复合材料冲击强度达25.31 kJ/m2,提高了34.56%.     

Room Temperature Curing Epoxy Adhesives for Elevated Temperature Service. Part III. The Effect of Silane Coupling Agents

The effect of silane coupling agents incorporated into the bulk of previously-developed room-temperature-curing epoxy adhesives^8,9,10 was studied. The physical and mechanical properties of corresponding aluminum bonded joints were characterized in ambient and humid-hot environments. Experimental results have demonstrated significant advantages of silane addition to the performance of these epoxy adhesives, especially under exposure to humid atmosphere. Thermal analysis of the polymerization processes, taking place during curing of the various low-temperature-curing formulations containing silane coupling agents, indicates that curing is not complete after seven days at room temperature, showing an exotherm at 80-100°C and a residual small one at 120°C. The basic formulation, comprising a tetra- and trifunctional epoxy resin blend and a multifunctional amine and ATBN cross-linking mixture, developed a three-phase matrix-rubber microstructure when the silane was added to the system.     

石墨烯改性对环氧树脂/碳纤维复丝拉伸性能的影响

采用直接分散法和上浆剂法分别制备了环氧树脂/碳纤维复丝,通过红外光谱、分光光度法等分析方法对处理的石墨烯的表面官能团及表面形貌进行表征,借助扫描电子显微镜对碳纤维表面进行微观形貌观察,研究了石墨烯改性对环氧树脂/碳纤维复丝界面性能的影响。结果表明:石墨烯表面成功地接枝了硅烷偶联剂KH-560;接枝硅烷偶联剂KH-560的石墨烯的环氧树脂/碳纤维复丝的拉伸性能优于未经改性的石墨烯的复丝;上浆法制得的环氧树脂/碳纤维复丝的拉伸性能优于分散法制得的复丝的拉伸性能;上浆剂法制备的石墨烯改性的环氧树脂/碳纤维复丝的断裂强力比未经过改性的未上浆的复丝的提高了48.6%,拉伸强度提高了30.4%,断裂伸长率提高了90.9%。     

钛酸钾晶须及硫酸钙晶须改性环氧树脂

应用硅烷及钛酸酯等偶联剂对钛酸钾晶须及硫酸钙晶须进行表面处理，考察晶须对环氧树脂力学性能、工艺性等的影响。研究表明，钛酸钾晶须经硅烷偶联剂处理后，能很好地改善复合材料的性能，硅烷的表面处理效果较钛酸酯的好。钛酸钾晶须添加到环氧树脂中后，材料的弯曲强度随晶须含量增大逐渐增大，在晶须含量为8％时达到最大值，之后性能稍有下降；材料的弯曲模量随晶须添加量的增加逐渐增大，冲击强度稍有降低。体系中添加硫酸钙晶须后，材料的性能也得到一定程度的提高。硫酸钙晶须对环氧树脂工艺性的影响较钛酸钾晶须小。SEM表明，晶须经合适的偶联剂表面改性后，与树脂基体的界面粘接得到有效改善。     

Room Temperature Curing Epoxy Adhesives for Elevated Temperature Service. Part III. The Effect of Silane Coupling Agents

The effect of silane coupling agents incorporated into the bulk of previously-developed room-temperature-curing epoxy adhesives^8,9,10 was studied. The physical and mechanical properties of corresponding aluminum bonded joints were characterized in ambient and humid-hot environments. Experimental results have demonstrated significant advantages of silane addition to the performance of these epoxy adhesives, especially under exposure to humid atmosphere. Thermal analysis of the polymerization processes, taking place during curing of the various low-temperature-curing formulations containing silane coupling agents, indicates that curing is not complete after seven days at room temperature, showing an exotherm at 80-100°C and a residual small one at 120°C. The basic formulation, comprising a tetra- and trifunctional epoxy resin blend and a multifunctional amine and ATBN cross-linking mixture, developed a three-phase matrix-rubber microstructure when the silane was added to the system.     

表面改性硅灰石增韧环氧树脂的研究

采用硬脂酸和两种硅烷偶联剂分别对硅灰石进行了表面改性,研究了不同改性剂的改性效果及不同用量的改性硅灰石对环氧树脂复合材料力学性能的影响;并对硅灰石增韧环氧树脂复合材料冲击断面形貌进行了分析。结果表明:硬脂酸改性硅灰石的改性效果最好,其改性表面接触角最大可达140°,与环氧树脂的相容性得到改善,复合材料的韧性明显提高。当硬脂酸改性硅灰石用量为环氧树脂质量的10%时,拉伸强度提高47.79%,冲击强度提高47.95%。     

Effect of coupling agents on the mechanical properties of mica/epoxy and glass fiber/mica/epoxy composites

The effect of coupling agents, two silane and one zirconate, on the mechanical properties of mica/epoxy and glass fiber/mica/epoxy composites has been investigated. The results showed that tensile modulus and flexural strength and modulus values were improved by the surface treatment of the coupling agents. The property retention was also found to be better in the case of coupling agent-treated mica/epoxy samples after boiling in water for 2h. In the case of glass fiber/mica/epoxy composites, the flexural modulus and interlaminar shear strength values improved with increase in mica content, but the effect of coupling agents was not pronounced.     

Using a localized fluorescent dye to probe the glass/resin interphase

A novel technique has been developed to study the buried polymer/substrate interfacial regions by localizing a fluorescent probe on the substrate surface. Epoxy functional multi‐layers of silane coupling agents were deposited on glass and doped with small amounts of a fluorescently labeled silane‐coupling agent (FLSCA). When the dye‐doped silane layers were immersed in an epoxy/amine cured resin, a blue shift in the emission maximum was measured after resin cure. Silane layers of varying thickness were tested. Thicker layers showed smaller fluorescence shifts during cure, suggesting incomplete resin penetration into these layers. The fluorescence sensitivity to the interfacial reaction was verified with external reflection Fourier Transform Infrared Spectroscopy (FTIR) of the silane layers immersed only in the amine hardener.     

UPR/苎麻布/碱式硫酸镁晶须复合材料Ⅰ——偶联剂处理晶须对复合材料力学性能的影响

选用钛酸酯偶联剂NDZ101、NDZ401和硅烷偶联剂KH550、KH570分别对碱式硫酸镁晶须进行预处理,采用模压工艺制备不饱和聚酯树脂/苎麻布/碱式硫酸镁晶须复合材料,研究了偶联剂加入比例对复合材料力学性能的影响。结果表明:除了KH570外,其他几种偶联剂均可保持或提高复合材料的拉伸强度和冲击强度;除了NDZ101之外,其他几种偶联剂均可提高复合材料的弯曲强度,当选用2%的KH550进行处理时,复合材料的弯曲强度最高,达到104.78 MPa,较未经偶联剂处理的复合材料的弯曲强度(95.18 MPa)提高了10.09%;利用硅烷类偶联剂处理晶须,对复合材料的拉伸模量、弯曲模量的改善效果优于钛酸酯类偶联剂;偶联剂处理不能改变复合材料脆性断裂的性质。     

Flexural and Charpy impact behaviour of epoxy/glass fabric treated by nano-SiO2 and silane blend

A sizing formulation, containing compatible and incompatible silane coupling agents with epoxy resin in conjunction with nanoscale colloidal silica, was used to modify the surface of glass fabric. The modified glass fabric/epoxy resin composite panels were fabricated and characterised by flexural test, Charpy impact test and scanning electron microscope (SEM). By combining nano silica with silane blend in the fabric sizing, more energy was consumed under bending and impacting, which resulted in an improvement of the toughness in composites. The flexural strength, bending stain and Charpy impact strength of the epoxy composite/glass fabric treated with 1?wt-% nano silica and silane blend were ～42, ～22 and 35%, respectively, higher than those of silane blend coated glass fabric-reinforced composites (without nano silica). Furthermore, the change of the brittle fracture of the composite into ductile fracture was investigated by SEM micrographs. A possible toughening mechanism was also proposed.     

Effect of silane coupling agents on basalt fiber–epoxidized vegetable oil matrix composite materials analyzed by the single fiber fragmentation technique

The fiber–matrix interfacial shear strength (IFSS) of biobased epoxy composites reinforced with basalt fiber was investigated by the fragmentation method. Basalt fibers were modified with four different silanes, (3‐aminopropyl)trimethoxysilane, [3‐(2‐aminoethylamino)propyl]‐trimethoxysilane, trimethoxy[2‐(7‐oxabicyclo[4.1.0]hept‐3‐yl)ethyl]silane and (3‐glycidyloxypropyl)trimethoxysilane to improve the adhesion between the basalt fiber and the resin. The analysis of the fiber tensile strength results was performed in terms of statistical parameters. The tensile strength of silane‐treated basalt fiber is higher than the tensile strength of the untreated basalt fiber; this behavior may be due to flaw healing effect on the defected fiber surfaces. The IFSS results on the composites confirm that the interaction between the fiber modified with coupling agents and the bio‐based epoxy resin was much stronger than that with the untreated basalt fiber. POLYM. COMPOS., 36:1205–1212, 2015. © 2014 Society of Plastics Engineers