本文選題：聚酰亞胺 + 不對(duì)稱��； 參考：《南昌大學(xué)》2017年碩士論文

【摘要】：傳統(tǒng)芳香族聚酰亞胺具有優(yōu)異的耐熱性和耐腐蝕性等性能,被廣泛應(yīng)用于航天航空、汽車電子、石油化工等領(lǐng)域。隨著科學(xué)技術(shù)的發(fā)展,在現(xiàn)代信息科技領(lǐng)域中,聚酰亞胺材料經(jīng)過技術(shù)的突破及材料的創(chuàng)新促使微電子產(chǎn)品趨于多功能化、高性能化、便攜化和柔性化。為了解決高密度、高精度環(huán)境下集成電路中所形成的信號(hào)延誤缺失及功率損耗發(fā)熱等問題,以及滿足柔性可穿戴設(shè)備的應(yīng)用需求,新一代高性能低介電、高透明無色等功能化材料的開發(fā)迫在眉睫。聚酰亞胺作為在微電子行業(yè)重要的應(yīng)用材料,如何開發(fā)出新型低介電及高透明的聚酰亞胺材料一直是高性能聚酰亞胺研究的重要課題之一。傳統(tǒng)聚酰亞胺材料一般都有較高的介電常數(shù)及較深的顏色,從結(jié)構(gòu)上分析是由于分子鏈間存在較強(qiáng)的相互作用,分子內(nèi)電荷的轉(zhuǎn)移使得給電子體與受電子體容易形成絡(luò)合物(CTC)。要獲得高透無色以及低介電常數(shù)的聚酰亞胺材料,就應(yīng)該減少CTC效應(yīng)的形成。為此,我們?cè)O(shè)計(jì)了含不對(duì)稱結(jié)構(gòu)的芐基,以及三氟甲基結(jié)構(gòu)引入到聚酰亞胺主鏈中來優(yōu)化其性能,主要從以下兩個(gè)方面來進(jìn)行探索研究:第一,以對(duì)羥基苯甲醛為初始原料,經(jīng)過三步反應(yīng)成功的得到含不對(duì)稱結(jié)構(gòu)的新型二胺4-氨基苯基對(duì)(4-氨基苯氧基)芐基醚(APABE)單體。通過所得新型二胺 APABE 和 1,4,4-三苯二醚二胺(1,4,4-APB)分別與 6FDA、ODPA、BTDA、BPDA四種芳香族二酐單體聚合得到不對(duì)稱與對(duì)稱的兩種聚酰亞胺,分別命名為API1-API4和SPI1-SPI4,并對(duì)這兩個(gè)系列進(jìn)行了全面的性能測試。對(duì)比發(fā)現(xiàn),API系列的溶解性和光學(xué)性能都明顯強(qiáng)于SPI系列。在熱性能和機(jī)械性能中,API系列和SPI系列的玻璃化轉(zhuǎn)變溫度分別為237-265 ℃和249-313 ℃,在氮?dú)猸h(huán)境中5%熱失重的溫度為453-486 ℃和511-517 ℃;拉伸強(qiáng)度分別為88.2-99.5 MPa和84.4-99.7 MPa。這說明含芐基的引入維持了聚酰亞胺良好的熱性能和機(jī)械性能。此外,在動(dòng)態(tài)介電分析中,API3的介電常數(shù)(ε) 2.57 (1 MHz和25℃)與介電損耗值(ε") 0.0040都比SPI3的介電常數(shù)(ε) 3.22 (1 MHz和25℃)與介電損耗值(ε")0.1376低。這表明不對(duì)稱結(jié)構(gòu)的引入也賦予了 CPI3較低的介電性能。第二,首先以2,2,2-三氟苯乙酮和苯乙酮為原料,分別與苯酚及氯化偏苯三酸酐兩步反應(yīng)得到含氟與不含氟的兩種二酐單體1,1-二(4-偏苯三酸酐單酯苯基)-1-苯基-2,2,2-三氟乙烷(TAMPPTE)和1,1-二(4-偏苯三酸酐單酯苯基)-1-苯基-乙烷(TAMPPE)。利用新型含氟二酐TAMPPTE和不含氟二酐TAMPPE分別與四種芳香族二胺ODA、1,4,4-APB、1,3,4-APB、DMB聚合得到含氟與不含氟的兩種聚酰亞胺,分別命名為FPI1-FPI4和NPI1-NPI4。同樣的對(duì)這兩個(gè)系列進(jìn)行了比較全面的性能測試。其中溶解性方面,FPI系列明顯優(yōu)于NPI系列。在光學(xué)性能及熱性能方面,FPI系列和NPI系列在T500處的透過率分別在93.3-95.7%和92.4-95.2%范圍內(nèi);玻璃化轉(zhuǎn)變溫度分別在230-285℃和228-284℃范圍內(nèi)。這說明FPI系列呈現(xiàn)出了更好的光學(xué)性能和熱性能。在介電分析中,FPI1和FPI3的介電常數(shù)(ε')分別為2.56和2.31(1 MHz和25℃),相對(duì)于商業(yè)化的Kapton(?)膜來說有很大的降低。這表明含三氟甲基結(jié)構(gòu)的FPI提高了材料的介電性能。
[Abstract]:With excellent heat resistance and corrosion resistance, the traditional aromatic polyimides are widely used in aerospace, automotive electronics, petrochemical and other fields. With the development of science and technology, in the field of modern information technology, the breakthrough of technology and the innovation of materials make microelectronic products more versatile in the field of modern information technology. High performance, portable and flexible. In order to solve the problems of lack of signal delay and power loss heating in integrated circuits in high density and high precision environment, as well as the application demand of flexible wearable equipment, the development of a new generation of high-performance, low dielectric, high transparent and colorless materials is imminent. How to develop new low dielectric and high transparent polyimide materials is one of the most important topics in the research of high performance polyimides. The traditional polyimide materials usually have high dielectric constant and deeper color. The structure analysis is due to the strong phase between the molecular chains. Interaction, the transfer of intramolecular charge makes it easy to form a complex (CTC) for electrons and electrons. To obtain polyimide with high colorless and low dielectric constant, the CTC effect should be reduced. Therefore, we have designed the benzyl group containing asymmetric structure and three fluoromethyl structure into the main chain of polyimide. In order to optimize its performance, we mainly explore the following two aspects: first, a new two amine 4- amino benzyl benzyl ether (APABE) monomer (4- amino Benzoxy) benzyl ether (APABE) monomer containing asymmetric structure was successfully obtained by the three step reaction of P hydroxybenzaldehyde as the initial raw material. The new type of amine APABE and 1,4,4- three benzene two ether two amine (1,4,4) were passed through. -APB) obtained asymmetric and symmetrical two Polyimides with four aromatic two anhydride monomers of 6FDA, ODPA, BTDA, BPDA respectively, named API1-API4 and SPI1-SPI4 respectively, and carried out a comprehensive performance test for the two series. It was found that the solubility and optical properties of the API series were obviously stronger than that of the SPI series. In the performance, the glass transition temperature of API series and SPI series is 237-265 C and 249-313 C respectively. The temperature of 5% heat loss in nitrogen environment is 453-486 and 511-517, and the tensile strength is 88.2-99.5 MPa and 84.4-99.7 MPa. respectively. In dynamic dielectric analysis, the dielectric constant (E) 2.57 (1 MHz and 25 C) and dielectric loss value (E) 0.0040 of API3 are lower than the dielectric constant (E) 3.22 (1 MHz and 25 C) and dielectric loss value (epsilon) 0.1376 of SPI3. This indicates that the introduction of asymmetric structure also gives CPI3 a lower dielectric property. Second, firstly, 2,2,2- three fluorophenone and benzene. Acetone is used as a raw material, and two kinds of two anhydride monomers 1,1- two (4- partial benzene three anhydride monoester) -1- -2,2,2- three fluoroethane (TAMPPTE) and 1,1- two (4- partial benzene anhydride monoester phenyl) -1- phenyl ethane (TAMPPE) are obtained respectively with phenol and chlorinated benzyl anhydride, respectively. The new fluorine two anhydride TAMPPTE and fluorine free two are obtained. Anhydride TAMPPE copolymerization with four aromatic two amines, ODA, 1,4,4-APB, 1,3,4-APB, DMB to obtain two kinds of polyimides containing fluorine and non fluorine, named FPI1-FPI4 and NPI1-NPI4., respectively. The two series have been tested in a more comprehensive performance. In terms of solubility, FPI series is obviously superior to NPI series. In optical properties and thermal properties The transmittance of the FPI series and the NPI series at T500 is within the range of 93.3-95.7% and 92.4-95.2%, respectively, and the glass transition temperature is within the range of 230-285 and 228-284, respectively. This shows that the FPI series presents better optical and thermal properties. In dielectric analysis, the dielectric constant (E) of FPI1 and FPI3 is 2.56 and 2.31 (1 MHz and 2, respectively). 5 degrees centigrade), which is much lower than that of commercialized Kapton film. This indicates that the FPI containing three fluoromethyl structure improves the dielectric properties of the material.
【學(xué)位授予單位】：南昌大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O633.2

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 夏森林;易龍飛;孫振;向詰然;汪映寒;;側(cè)鏈含鄰苯二甲酰亞胺的聚酰亞胺液晶垂直取向劑的制備與表征[J];高分子學(xué)報(bào);2013年11期

2 卜倩倩;張樹江;楊逢春;李彥鋒;;不對(duì)稱聚酰亞胺的結(jié)構(gòu)設(shè)計(jì)、合成及其可溶性[J];化工新型材料;2011年04期

3 宋曉峰;;聚酰亞胺的研究與進(jìn)展[J];纖維復(fù)合材料;2007年03期

4 李福成;;聚酰亞胺/無機(jī)納米復(fù)合材料的制備、結(jié)構(gòu)與性能[J];工程塑料應(yīng)用;2006年04期

5 王維;張愛清;邱小林;楊志蘭;喬學(xué)亮;陳建國;;含氧膦結(jié)構(gòu)的可溶性感光聚酰亞胺合成與表征[J];高分子學(xué)報(bào);2006年03期

6 尹大學(xué),李彥鋒,張樹江,王曉龍,胡愛軍,范琳,楊士勇;聚酰亞胺材料溶解性能的研究進(jìn)展[J];化學(xué)通報(bào);2005年08期

7 崔永麗,張仲華,江利,歐雪梅;聚酰亞胺的性能及應(yīng)用[J];塑料科技;2005年03期

8 景曉輝,馬海燕;一種醚酐型可溶性聚酰亞胺的合成與表征[J];化工新型材料;2005年05期

9 劉金剛,楊海霞,王麗芳,李彥峰,范琳,楊士勇;含氟芳雜環(huán)高分子及其在微電子工業(yè)中的研究進(jìn)展[J];高分子通報(bào);2003年05期

10 褚慶輝,丁孟賢;主鏈含有β-二酮結(jié)構(gòu)聚酰亞胺的合成與表征[J];應(yīng)用化學(xué);1999年06期

，

本文編號(hào)：2066235