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1、 低介电常数功能化聚降冰片烯的合成及性能的研究低介电常数功能化聚降冰片烯的合成及性能的研究 摘摘 要要 本文在钯金属催化剂下通过乙烯基加成聚合反应合成了三类聚合物： 降冰片烯二醇酯类聚合物、降冰片烯二羧酸酯类聚合物和降冰片烯酰亚胺类聚合物。用红外、核磁以及 GPC 等对单体及其聚合物的结构进行了表征。同时还对聚合物的溶解性、玻璃化转变温度、热稳定性和介电常数等性能进行了研究，并得到了以下结果： 降冰片烯二羧酸酯类聚合物和降冰片烯二醇酯类聚合物在有机溶剂中都有很好的溶解性。 而降冰片烯酰亚胺类聚合物在有机溶剂中的溶解性不如降冰片烯二羧酸酯类聚合物好。 利用DMA得到了降冰片烯二羧酸酯类聚合物和降
2、冰片烯二醇酯类聚合物的玻璃化转变温度，同时利用Maxwell 公式计算得到了聚合物的介电常数。这两类聚合物的玻璃化转变温度和介电常数都随着侧链长度的增加而降低， 但相同侧链长度的降冰片烯二醇酯类聚合物的玻璃化转变温度和介电常数要比降冰片烯二羧酸酯类聚合物低一些。 利用热失重对降冰片烯二羧酸酯类聚合物和降冰片烯酰亚胺类聚合物的热学性能和热分解行为进行了研究， 降冰片烯二羧酸酯类聚合物的热分解温度能达到 330以上。而降冰片烯酰亚胺类聚合物起始热分解温度高达 430以上，比未取代的聚降冰片烯的高。并且获得了降冰片烯二羧酸酯类聚合物和 N-金刚烷基-降冰片烯酰亚胺的表观活化能及热分解机理的模型。发现
3、降冰片烯二羧酸酯类聚合物热分解温度和表观活化能均随着侧链长度的增加而降低。 以降冰片烯二醇丙酯和 N-环已基-降冰片烯酰亚胺为例，考察了聚合条件对聚合结果的影响，分别在侧链的长度，单体和催化剂的摩尔比，溶剂的极性，反应时间，反应温度等方面方面对单体的聚合进行了研究。 关键词关键词：功能化聚降冰片烯，降冰片烯衍生物，加成聚合，钯金属催化剂，介电常数，热稳定性，溶解性1 LOW DIELECTRIC CONSTANT OF FUNCTIONALIZED POLYNORBORNENE: SYNTHESIS AND PROPERTIES ABSTRACT Three kinds of polymers
4、: poly(norbornene dimethyl dicarboxylate)s, poly(norbornene dicarboxylic acid dialkyl ester)s, and poly(N-substituted nadimide)s, were synthesized by vinyl addition polymerization using palladium(II)-based catalyst from pure exo-monomers, and their structures were characterizated with IR,1H-NMR and
5、GPC etc.The solubility, the glass transition temperatures, the thermal properties and degradation behaviors and the dielectric constants were also investigated and the results were summarized as follows: The resulting polymers such as poly(norbornene dicarboxylic acid dialkyl ester)s (alkyl = Me (PN
6、B-1), Et (PNB-2), Pr (PNB-3) and Bu (PNB-4), poly(norbornene dimethyl dicarboxylate)s, (carboxylates = acetate (PNB-A), propionate (PNB-B), and butyrate (PNB-C) showed good solubility in common organic solvents. The solubility in common organic solvent of poly(N-substituted nadimide)s were not as we
7、ll as poly(norbornene dimethyl dicarboxylate)s and poly(norbornene dicarboxylic acid dialkyl ester)s. The glass transition temperatures of polynorbornene esters were characterizated by DMA. We also gained refractive indexs of polymers, and calculated the dielectric constants of polymers by Maxwell e
8、quation. The glass transition temperatures and dielectric constants of solid polymers were found to decrease as the alkyl side-chain length increases for both polymer series. However, poly(norbornene dimethyl dicarboxylate)s showed lower glass transition temperatures and higher dielectric constants,
9、 compared with those of poly(norbornene dicarboxylic acid dialkyl ester)s containing the same carbon number of side chain. The thermal properties and degradation behaviors of poly(norbornene dicarboxylic acid dialkyl ester)s and poly(N-substituted nadimide)s were investigated by thermogravimetric an
10、alysis in dynamic conditions, the first one high thermal stability up to 330, the later one show higher thermal stability up to 430. 2 3 The apparent activation energy and thermal degradation model of poly(norbornene dicarboxylic acid dialkyl ester)s and poly(N-substituted nadimide)s were also estim
11、ated repectively. The thermal degradation temperture and the apparent activation energy of poly(norbornene dicarboxylic acid dialkyl ester)s decreases in the order PNB-1PNB-2PNB-3PNB-4 with the increase in size of side chain. The effects of polymerization conditions on the polymerization results by
12、polymerizing norbornene dimethyl propionate and N-cyclohexyl-nadimide were systematically investigated, such as the size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of monomers. It was found the polar properties of solv
13、ents have considerable effect on the catalyst activity. KEYWORDs: functionalized polynorbornene, norbornene derivatives, vinyl addition polymerization, palladium()catalyst, thermal stability, dielectric constant, solubility, glass transition2 河北工业大学硕士学位论文 第一章第一章 绪论绪论 1-1 前言前言 随着超大规模集成电路（ULSI）器件集成度的提
14、高，元件极小尺寸向深亚微米发展，当器件特征尺度逐渐减小时，由于多层布线和逻辑互连层数增加1，导线间电容和层间电容以及导线电阻增加，从而使得导线电阻R和电容C产生的RC延迟会有所上升2-5。当特征尺寸下降到 0.5 微米或更小时，互连线延迟则成为一个决定整个门延迟主要因素。如图 1.1 所示6，在 0.25 微米的元件尺寸大小时，50%的元件速度延迟，将来自于由内连线所造成的时间延迟（RC time delay)7。由内连线所造成的时间延迟，为金属导线的电阻值（R）与金属导线间介电层的电容值（C）所得乘积，因此欲减少內连线的时间延迟有两个方法为了降低RC延时及功率损耗，除了采用低电阻率金属(如铜
15、)替代铝外8-9，重要的是降低介质层带来的寄生电容C。由于C正比于介电常数，所以就需要开发新型的低介电常数（）材料10-16来作为绝缘材料。而目前普遍采用的介电材料SiO2（=3.94.2）已经不能满足ULSI发展的需求，所以多年来人们一直都在努力寻找各种合适的低介电常数材料。 图 1.1 信号延迟与器件尺寸的关系 Fig.1.1 Dependence of signal delay on device size 最近十年，有机聚合物电介质材料由于具有介电常数低（一般为 2.62 左右） ，填隙性能好，平坦化能力高和残余应力小的优点，其研究倍受人们关注，国内外已进行了很好的综述17-26。随着
16、铜布线工艺的推广，集成电路工艺温度将进一步降低，这将为有机薄膜在ULSI中的广泛应用提供更为有利的条件。在未来最高加工温度为 350的集成电路工艺中。同时，有机高分子材料可以采用旋涂式(spin-on glass)代替传统的沉积式制造器件，这样可以大幅地降低制造成本。因此在未来深亚微米集成电路中，采用有机聚合物作为绝缘层介质是很有可能的也是很有必要的27-28。 1低介电常数功能化聚降冰片烯的合成及性能的研究 1-2 降冰片烯降冰片烯 降冰片烯（norbornene, NBE）化合物的聚合可通过自由基聚合或阳离子聚合、开环易位聚合和加成聚合等几种方式进行29-31，所得聚合物的结构、性能取决于聚合方法和催化剂的选择32。自由基聚合得到产物的分子量低，发生重排，聚合反应速度慢33, 34。开环聚合所得聚合产物中存在不稳定的双键，使其耐老化性较差35, 36。 NBE加成聚合仅仅打开环上的键而不会发生开环反应， 聚合物
