环氧-有机硅树脂新型固化剂的研制

研究了硅酸酯对有机胺固化剂的化学改性反应，制备了一种适用于环氧-有机硅树脂的新型固化剂，并对改性产物的结构与性能进行了研究，结果表明，此种固化剂不仅改善了环氧-有机硅树脂的室温固化性及树脂固化膜的表面疏水性，而且很大程度上提高了该种树脂对金属基体的附着强度。     

环氧树脂化学改性有机硅树脂的方法综述

环氧改性有机硅树脂可提高有机硅树脂的力学性能和粘接性能,还可降低有机硅树脂的固化温度.归纳总结了环氧树脂化学改性有机硅树脂的4种反应类型:1)缩聚反应;2)环氧基的开环聚合反应;3)硅氢加成反应;4)引入环氧基的反应.对该领域的近期研究成果进行了简要的综述,并展望了该领域未来的发展方向.     

新型有机硅材料的制备与性能

[2-(3,4-环氧环己基)乙基]三甲氧基硅烷和二苯基硅二醇进行缩聚反应制备出含苯基和环氧基的高折光指数有机硅树脂,并通过傅里叶变换红外光谱和核磁共振对其结构进行了表征。该树脂与甲基六氢苯酐固化后得到透明的有机硅封装材料,测试结果表明:该有机硅封装材料具有较高的折光率(1.545),较高的透光率(90%),优异的黏结性,良好的耐热性能以及力学性能,可用于发光二极管封装领域。     

真空灌注用混合型聚醚胺/环氧树脂固化动力学

采用红外光谱比较了混合型固化剂/环氧树脂体系与单一固化剂体系固化速度的差异,通过非等温示差扫描量热法研究了混合型聚醚胺/环氧树脂体系的固化动力学,采用Kissinger方程、Crane方程确定固化动力学参数,并通过外推法确定树脂体系的固化制度。结果表明,混合型固化剂体系反应4 h时固化程度达到79.4%,较单一固化剂体系,固化速度明显加快。因Crane方程求出的反应级数与实验结果相差较大,故采用线性拟合法确定树脂体系的反应级数为1.694,外推法确定了树脂体系的固化制度为65℃/2 h+100℃/1 h+150℃/30 min。     

硅氢基与乙烯基比例对大功率LED封装用有机硅树脂固化行为的影响

选用端乙烯基苯基硅油为基础树脂,含氢苯基硅油为固化剂,铂络合物为催化剂制备了发光二极管(LED)封装用有机硅树脂。用非等温差示扫描量热分析法研究了硅氢基与乙烯基比例对有机硅树脂的固化行为的影响。结果表明,硅氢基与乙烯基比例为1.6时,固化温度最低,即反应条件最为温和;确定固化工艺为真空脱泡后前段固化温度为80 ℃/1 h,而后95 ℃/2 h。     

搪塑模具制备中电镀用环氧树脂芯模固化过程的流变动力学研究

搪塑模具制备过程中电镀用环氧树脂芯模的固化过程对于搪塑模具的制备至关重要。今采用流变学的的方法,对电镀用环氧树脂芯模的固化过程进行了研究。环氧树脂芯模在固化过程中,双酚A型环氧树脂与多元胺固化剂进行交联反应,固化程度逐渐增大。固化程度先缓慢增加,然后迅速增加,最后缓慢增加接近最大值,芯模完全固化。同时,温度对固化速率影响也很大。温度越高,速率越大;温度越低,速率越小,完全固化所用时间也就越长,则树脂芯模可操作加工时间也就越长。研究建立了电镀用环氧树脂的固化反应动力学方程,得到温度与固化速率的关系,同时获得固化反应的活化能,结果表明电镀用环氧树脂的固化反应动力学符合Kamal自催化动力学模型。     

NH-POSS基耐高温环氧树脂的制备及动力学分析

环氧树脂耐高温基体在航空航天、特种涂料、电气及半导体电子等高新技术领域得到了广泛的应用。环氧树脂的性能在很大程度上受环氧树脂固化剂的影响,对比了三种不同胺固化剂对环氧树脂固化的影响,结果显示实验室自制的NH-POSS固化剂优于脂肪族和芳香族类胺固化剂,NH-POSS固化剂可以提高整个固化体系的耐高温性能,使其玻璃化转变温度高达234℃,是一种耐高温树脂。采用n级反应理论的动力学模型,并对热力学数据进行分析,拟合出了NH-POSS环氧树脂体系的固化工艺条件,为NH-POSS固化环氧树脂的加工工艺提供了理论依据。     

SnO2改性TiO2光催化涂料的制备及性能测试

以SnO2改性TiO2为光催化剂，有机硅改性丙烯酸树脂为基料，聚氨酯为固化剂，制备了室温固化光催化余料。采用XPS、EDS、SEM对其进行表征，考察了涂料的光催化活性、pH值的影响及反应动力学。     

双酚A型环氧树脂/芳香胺固化体系的固化动力学研究

分别以4,4‘-二氨基二苯甲烷（DDM）和4,4‘-二氨基二苯砜（DDS）为固化剂，采用非等温差示扫描量热法（DSC）研究了E-44和E-51两种双酚A型环氧树脂的固化反应动力学。收集与分析了在25～350℃范围内分别以5、10、15、20℃/min的升温速率进行固化的反应参数，然后采用Starink法计算得到不同环氧固化体系的表观活化能。同时，借助各固化体系的动态流变性能，分析了双酚A型环氧树脂/芳香胺固化体系的固化反应机理，并选用双参数自催化模型计算了各固化体系的反应速率方程。研究结果表明：当环氧固化体系的固化剂不同时，采用DDM作为固化剂的环氧固化体系（E-44/DDM、E-51/DDM），其表观活化能均低于添加DDS固化剂的环氧体系；选用同种固化剂（DDM或DDS）时，E-51树脂体系的表观活化能均低于E-44树脂固化体系。反应速率方程结果显示，该双参数自催化模型与实际试验结果的吻合性良好，可用于描述双酚A型环氧树脂/芳香胺固化体系的固化历程。     

含硅芳炔树脂热裂解行为及动力学

用热失重法(TGA、DTG)分析了含硅芳炔树脂固化物的热裂解动力学,并用Kissinger和Ozawa法计算出含硅芳炔树脂固化物的热裂解的表观活化能分别为149kJ/mol和153kJ/mol,热裂解反应近似于一级反应,据此建立了热裂解的动力学模型。用热裂解-气相色谱-质谱联用(Py-GC-MS)方法对含硅芳炔树脂的热裂解气相产物进行了分析,在热裂解过程中,主要有甲烷、氢气、乙烷、乙烯、水等气体放出。用拉曼光谱、X-射线衍射等分析了含硅芳炔树脂固化物热裂解的残留物结构,残留物是以无定型碳、石墨、SiC为主要成分的陶瓷化结构。     

脲醛树脂的固化研究

通过缩聚法制备出脲醛树脂,考察了制备单组分固化剂NH4C l、2%HC l、5%的H3PO4、H2O2及双组分固化剂NH4C l和2%HC l、NH4C l和5%H3PO4的使用条件,并确定了复合固化剂的配比和用量。发现双组分固化剂固化时间适宜,固化效果好。     

腰果酚缩醛胺固化剂的性能研究

以腰果酚、甲醛和二乙烯三胺为原料经缩聚反应合成了腰果酚缩醛胺(PCD)固化剂,采用红外光谱对产物结构进行了表征。与目前国内几种常见的环氧树脂固化剂对比研究了其与环氧树脂的相容性、固化物的物理力学性能、耐化学介质性及对不理想表面的附着力。实验结果表明,PCD固化剂具有良好的综合性能。     

新型快速固化环氧树脂胶粘剂的制备及性能

以己二酸、多胺(如二乙烯三胺、三乙烯四胺或多乙烯多胺等)为原料,采用熔融缩聚法合成了3种低黏度、低毒性且可室温固化的环氧树脂(EP)胶粘剂用聚酰胺固化剂(PA1、PA2或PA3)。探讨了固化剂含量对EP胶粘剂的固化速率和粘接性能等影响,并采用单因素试验法优选出EP/固化剂的最佳配比。结果表明:EP胶粘剂的固化速率和剥离强度依次为EP/PA1胶粘剂>EP/PA2胶粘剂>EP/PA3胶粘剂;当m(PA1):m(EP)=0.6:1.0、w(促进剂)=1.0%(相对于EP质量而言)、固化温度为80℃和固化时间为60min时,相应胶粘剂的适用期较长,并且加热后能快速固化,而且用该胶粘剂制备的包封膜经处理后,其综合性能良好,可满足柔性印刷电路板(FPC)的生产要求。     

Effect of aromatic and aliphatic amines as curing agents in sulfone epoxy monomer curing process

The kinetics of the curing of sulfone epoxy (SEP) monomers using aromatic and aliphatic amine curing agents was studied via differential scanning calorimetry (DSC). SEP curing is a two-stage process involving SEP/electron donation and electron donation to either aliphatic or aromatic curing agents. The SEP/electron donation curing process occurred readily since semi-electron-withdrawing curing agents are induced by nucleophilic substitution in the first stage. In the second stage, SEP is cured by the semi-electron-withdrawing curing agents. The kinetic parameters of the curing process were determined using a conversional method derived from Ozawa’s and Kissinger’s methods, which are typically used for kinetic analysis of data for thermal treatments. The higher melting points and steric bulk of the aromatic curing agents resulted in higher curing activation energies than for the aliphatic curing agents. The aliphatic curing agents also increased the activation energy of the curing process due to their electron-withdrawing and cross-linking properties as well as the viscosity of the epoxy/amine curing system. Cured SEP/aromatic curing agent materials possessed higher glass transition temperatures than cured SEP/aliphatic curing agent materials.     

Gradient curing process in the mixed epoxy system and property analysis of the cured products

To improve the high-temperature mechanical properties of room temperature cured epoxy resin, a mixed curing agent was used and the curing process was studied under a temperature ramp. The tests including gelation time, differential scanning calorimetry, dynamic thermomechanical analysis, and flexural strength were taken to evaluate the changes in pot life, reaction process, heat resistance, and mechanical properties, respectively. The analysis then focused on the extent of cure. Meanwhile, the effects of non-reactive diluent on the curing process and product properties were analyzed. Results showed that the resin system containing the mixed curing agent possessed an exquisite characteristic when the temperature rose slowly to 363 or 393 K. The system could be preliminarily solidified in an hour and a half at normal temperature, and then in the heating-up environment, curing reactions initiated by different types of curing agents took place, caused the curing degree to exhibit certain gradient and increase to greater than 95% quickly. The glass transition temperature and the mechanical stability at high testing temperatures of the cured products were therefore improved. When dibutyl sebacate was added into the system as the diluent, the curing reaction was postponed, the curing degree was slightly increased; however, the glass transition temperature and mechanical properties at high temperatures were apparently decreased.     

基体树脂可被增韧能力的研究

分散的橡胶微球改性环氧树脂能产生良好的增韧效果。同种弹性微球对不同的环氧体系增韧程度却有不同，这取决于基体树脂的被增韧能力，选用了３种不同的弹性体和３种不同的环氧／固化剂体系进行实验，讨论了它们的增韧机理，提出了基体树脂可被增韧能力的３个内涵：（１）基体树脂产生微裂纹的能力；（２） 基体树脂的转为温度（３）在转变温度以上基体树脂的可屈服程度。     

中温固化EP体系研究进展

综述了近几年来中温固化环氧树脂(EP)体系的最新研究进展,详细介绍了双氰胺、酸酐和咪唑等常用固化剂及其促进剂的固化机制,最后对EP中温固化体系未来的研究方向进行了展望。     

Monitoring the curing process of reinforced plastics structures

The feasibility of monitoring curing processes in large reinforced plastics structures by electrical volume resistivity techniques has been studied. It has been found, by embedding electrodes and thermocouples within a heavy-walled structure during fabricaton and by monitoring the change is resistance during the curing process, that information indicative of the rate and extent of curing can be obtained. The resin system used in this study was Epon 826/MNA/BDMA.     

单组分环氧树脂胶粘剂的研究现状

综述了单组分环氧树脂胶粘剂的发展现状,介绍了湿气固化型、微胶囊包覆型、潜伏性固化剂型以及阳离子光固化等类型的单组分环氧胶的研究进展,重点讨论了潜伏性固化剂型环氧胶的改性方法及效果。     

户外像素管软质灌注胶的研制与应用

采用脂环族环氧树脂、柔韧性环氧树脂、改性脂环胺类固化剂为主要原料，研制出户外像素管灌注软胶，产品具有耐紫外线辐照、耐冷热冲击、粘接性好等特点。介绍其制备方法、性能及用。