【作者】 戴善凯；

【导师】 梁国正；

【作者基本信息】 苏州大学 ， 材料学， 2010， 硕士

【摘要】 随着电子工业的迅速发展,电子信息数据处理以及通信系统的电子整机产品不断地向多功能、微型化、集约化方向发展,要求作为电子元器件和电子产品关键基础材料的覆铜板（CCL）必须满足―高频、高速‖的信息处理与传输的目标,从而使得所制备的覆铜板不再仅仅具备支撑功能,而且兼具信号传输以及强化电子产品高可靠性的功能,这就意味着CCL用树脂基体必须具有优良工艺性、更高的力学性能和耐湿性、超低介电常数、低膨胀性等性能特点。氰酸酯（CE）树脂是一种具有优异的综合性能的树脂,在宽广的温度和频率范围有着低且稳定的介电常数（ε）和介电损耗正切值（tanδ）,高的耐热性和低的吸湿率等。然而其固化反应温度高、时间长以及固化后高度交联的三嗪环的脆性较大,限制了其在高频CCL领域的应用。本文采用对CE树脂固化有着良好催化活性的二月桂酸二丁基锡（DBTDL）和三羰基环戊二烯锰（CpMn（CO）₃）,设计了由DBTDL与CpMn（CO）₃按照不同配比组成的复配催化剂（HC）,研究了不同配比的HC对CE固化催化效应以及性能的影响。研究结果表明,HC对CE的固化有着高效的催化作用,且两种组分DBTDL和CpMn（CO）₃之间有着一定的协同作用,固化后的树脂有着高的耐热性及优异的介电性能;当DBTDL与CpMn（CO）₃的摩尔配比为1:20,即为HC2时,相比与未加催化剂的CE,CE/HC2的凝胶时间仅为CE的1/20,其DSC反应峰顶温度向低温方向移动了118.7℃,反应活化能仅为CE的1/2,达到了CE树脂可中温固化的目标;其固化后树脂的玻璃化转变温度（Tg）提高了14℃,并保持CE树脂原有的优异的介电性能与热稳定性。同时,本文展开探讨了不同含量的单一CpMn（CO）₃催化剂对CE树脂固化后的性能的影响,研究结果表明,随着CpMn（CO）₃催化剂含量的增加,其催化效应更加明显;当CpMn（CO）₃催化剂的含量为1.00wt%时,其力学性能、介电性能、耐热性等综合性能最为突出。针对CE树脂中高度交联的三嗪环脆性较大,将具有高的耐热与优异介电性能的环氧改性甲基苯基硅树脂（EPMPS）用来改性CE树脂,制备了高韧性低介电损耗的EPMPS-n/CE树脂,系统研究了改性CE树脂的固化反应性以及固化物的冲击强度、热性能、吸湿率和介电性能。研究结果表明,EPMPS不仅显著加速了CE单体的固化反应,而且有效提高了CE固化树脂的冲击强度和耐湿性。含15wt%EPMPS的改性树脂体系的冲击强度达17.8kJ/m²（约为纯CE树脂冲击强度的3倍）,吸水率和介电损耗正切值分别仅为纯CE树脂的50%和79%。将具有一定长径比的碳酸钙（CaCO₃）晶须引入CE树脂中,制备了CaCO₃-n/ CE复合材料,研究了材料的力学性能、热性能及介电性能等。研究结果表明,在CE树脂中加入经KH-550处理的CaCO₃晶须（记为CaCO₃（KH-550））,可以在保持CE树脂优异介电性能的基础上,提高树脂的弯曲强度、冲击强度及600℃的残碳率,并降低树脂的平均线膨胀系数。当CaCO₃（KH-550）晶须的含量为16wt%时,复合材料的弯曲强度和冲击强度分别达到最大值。更多还原

【Abstract】 With the rapid development of electronic industry, electronic information processing and communication electronic products have been going to the direction of multi-functions, micro-oriented and intension, suggesting that copper clad laminates （CCLs）, the key basic material of electronic components and electronic products, must meet the target of information processing and transmission with―high-frequency, high-speed‖. Hence CCLs play the role of supporting, but the transmission of signals and the enhancement of reliability on electronic products also, reflecting that the resin matrices for CCLs should possess excellent processing characteristics, high mechanical properties, good moisture resistance, low dielectric constant and loss as well as low expansion.Cyanate ester （CE） resin is a typical thermosetting resin with outstanding integrat properties including low and stable dielectric constant （ε） and loss tangent （tanδ） over wide temperature and frequency ranges, high heat-resistant and low moisture absorption. However, it needs to be cured at high temperature for a long time; moreover, the cured CE resin has poor toughness due to the presence of highly cross-linked triazine rings.The two drawbacks greatly limit the application in the field of high-frequency CCLs. In this thesis, a novel kind of hybrid catalysts （HC） consisiting of dibutyl tin dilaurate （DBTDL） and u.v. activated tricarbonyl cyclopentadienyl manganese （CpMn（CO）3） with different moral ratios were developed to catalyze the curing of CE. The catalytic effect of HC on the properties of CE was investigated. Results show that: HC has an attractive synergy effect on the curing of CE over its two separate components. In addition, cured HC/CE resins exhibit high thermal stability and outstanding dielectric properties. When the mole ratio of DBTDL and CpMn（CO）3 is 1:20, coded HC2, the gel time of CE/HC2 is only 1/20 as that of CE, the curing peak temperature in DSC curves shifts to low temperature with a gap of about 119℃; moreover the activity energy of CE/HC2 is only 1/2 as that of CE, suggesting that CE/HC2 can be cured at medium temperature. Interestingly, the glass transition temperature （Tg） of cured CE/HC2 resin is 14℃higher than neat CE resin, while dielectric and thermal properties of cured CE/HC2 resin is as the same as that of CE resin.Besides, the effect of the CpMn（CO）3 content on the properties of CE is investigated. Results show that the effect is much more obvious with the increase of CpMn（CO）3 content, when the content is 1.00wt%, the resultant CE resin has the best mechanical, dielectric and thermal properties.A novel resin system with improved toughness and low dielectric loss based on CE and epoxy modified methyl phenyl silicone （EPMPS）, coded as EPMPS-n/CE, was developed in this thesis. The curing behavior and the integrate properties such as impact strength, thermal and dielectric properties as well as water absorption are systematically investigated in detail. Results show that EPMPS can not only catalyze the curing reaction of CE, but also significantly improve the toughness and moisture-resistance of cured CE resin. In case of EPMPS/CE with 15wt%EPMPS, its impact strength is 17.8kJ/m2 （about 3 times of that of pure CE resin）. In addition, the water absorption and dielectric loss of the former are only about 50%, and 79% of those of pure CE resin, respectively.The calcium carbonate （CaCO₃） whiskers are introduced into CE resins to prepare CaCO₃-n/CE composites. The mechanical, thermal and dielectric properties of the composites are investigated. Results show that the addition of surface treated CaCO₃ whiskers by KH-550 （coded as CaCO₃（KH-550）） into CE resin can not only improve the flexural and impact strength as well the char yield at 600℃, but also decrease the average linear thermal expansion coefficient with the maintaining of outstanding dielectric and thermal properties of original CE resin. The composite with 16wt% CaCO₃（KH-550） has the maximum flexural and impact strengths.更多还原