Title

新穎型磷系不對稱聚醯亞胺與低介電Benzoxazine之製備

Translated Titles

Preparation of novel phosphinated unsymmetric polyimides and low-dielectric benzoxazine

DOI

10.6845/NCHU.2013.00042

Authors

許志光

Key Words

聚醯亞胺 ; 低介電 ; Polyimide ; Benzoxazine

PublicationName

中興大學化學工程學系所學位論文

Volume or Term/Year and Month of Publication

2013年

Academic Degree Category

碩士

Advisor

林慶炫

Content Language

繁體中文

Chinese Abstract

第一部分為以DOPO進行親核性加成於在酸催化下的四種雙酚,包含雙酚A、4,4’-異亞丙基雙(2,6-二甲基苯酚)’ 、9,9’-二(4-羥基苯基)芴、雙(4-羥基苯基)環己烷,得到磷系酚基單體(1-4),接著經由兩步製程,得到雙胺單體(9-12)。以單體(9-12)與ODA以及二酸酐進行聚合得到共聚醯亞胺,由於四種雙胺結構上有相似程度,我們將單體9所製備的聚醯亞胺來與單體10所製備的聚醯亞胺進行比較,單體11所製備的聚醯亞胺與單體12所製備的聚醯亞胺進行比較。含單體10的聚醯亞胺其結構上有較多的methyl官能基,因此比含單體9的聚醯亞胺有較高的玻璃轉移溫度、模數、尺寸安定性、接觸角度、溶解度等優點。而含單體11的聚醯亞胺其結構上的芴官能基比單體10的環己烷立體障礙較大、較剛硬,因此玻璃轉移溫度較高。 第二部分為以脂肪族雙胺,分別利用傳統一步法與兩步法合成Benzoxazine單體(2),藉由氫譜追蹤分析,發現以傳統一步法尚無法解決Triazine快速生成的問題,因此改用兩步法製備。將單體(2)與環氧樹脂(CNE、DCPDE)進行共聚,探討其性質。以吸水率以及介電儀分析,均顯示出含脂肪族結構的固化物因極性較低,有較低的吸水率以及較低的介電常數,以固化物(2)/DCPDE吸水率1.149%,介電常數2.75最為優異。

English Abstract

[Part 1] Four novel diamines (9-12) were prepared by a two-step procedure from phosphinated phenols (1-4), which were prepared from acid-fragmentation of four bisphenols, including Bisphenol A, 4,4′-isopropylidenebis(2,6-dimethylphenol), 9,9’-bis(4-hydroxyphenyl)fluorene, and cis(4-hydroxyphenyl)cyclohexane, followed by nucleophilic addition of 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Copolyimides based on (9-12)/ 4, 4’-diaminodiphenyl ether /dianhydride were prepared. Due to the structure similiarity, (9)-containing copolyimides are compared with (10)-containing copolyimide, while (11)-containing copolyimides are compared with (12)-containing copolyimide. The structure-property relationship on the copolyimides was discussed. (10)-Containing copolyimides with the tetramethyl substitutent display higer Tg, modulus, dimensional stability, contact angle, and better solubility than (9)-containing copolyimides. The fluorene structure make (11)-containing copolyimides exhibit higher Tg than (12)-contaiing copolyimides. [Part 2] An aliphatic benzoxazine (2) was prepared via one-pot and two-pot. By analysis of 1H-NMR of monomer (2), we found that monomer (2) prepared via one-pot still have triazine in cosolvent. Monomer (2) and epoxy(CNE/DCPDE) copolymerized in the curing system. The (2)/DCPDE thermoset has the lowest moisture absorption and dielectric constant due to the aliphatic group.

Topic Category 工學院 > 化學工程學系所
工程學 > 化學工業
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