Title

磷系氧代氮代苯并環己烷樹脂及其高性能硬化物

Translated Titles

Phosphinated Benzoxazines and Their High-Performance Thermosets

DOI

10.6845/NCHU.2011.00317

Authors

林宏澤

Key Words

氧代氮待苯并環己烷 ; 環氧樹脂 ; 難燃 ; benzoxazine ; epoxy resin ; flame retardancy

PublicationName

中興大學化學工程學系所學位論文

Volume or Term/Year and Month of Publication

2011年

Academic Degree Category

博士

Advisor

林慶炫

Content Language

英文

Chinese Abstract

本研究針對磷系benzoxazine樹脂的合成與性質進行一系列的討論,在內容部分共分為五個部分,包含磷系單官能benzoxazine的合成與應用,以及磷系雙官能benzoxazine的合成與衍生物應用等相關性質探討。 在第一部份,我們成功合成三種單官能磷系benzoxazine,有別於傳統低產率的製備方式,我們提出利用三步法合成方式,首先利用醛類與胺類先行反應,再導入DOPO進行還原,再以甲醛進行閉環而得,透過此方式總產率可大幅提昇。最後我們對單體進行一系列鑑定與分析,並將之與商用benzoxazine (F-a)進行共聚,並針對其固化物性質進行一系列討論。 在第二部分,我們採用一鍋法方式合成酚基含磷單官能benzoxazine,其產率可高達91%,並將之導入環氧樹脂以提高環氧樹脂的難燃性與熱機械性質,透過此改質方式環氧樹脂的總反應點數量不會隨改質而大幅損失,此外固化交聯後亦可保有優秀的玻璃轉移溫度。當磷含量達0.61%時,樹脂固化物即可通過UL-94 V-0難燃測試並,擁有高達245oC的Tg。 在第三部分,我們採用一鍋法合成磷系雙官能benzoxazine,透過一鍋法的合成方式其產率可高達95%,接著我們對單體進行一系列鑑定與分析並將之作為環氧樹脂的硬化劑,其環氧樹脂固化物具有相當低的熱膨脹係數與優異的難燃特性。 在第四部分,我們利用一系列benzoxazine與DOPO以一步法合成高純度含磷雙酚,透過鑑定與分析可以確定產物具有相當高的純度,並將之導入環氧樹脂以提升樹脂的難燃性,並可降低樹脂固化物的熱膨脹係數與吸水性。 在第五部分,我們利用一鍋法所製備出的酚基含磷單官能benzoxazine,直接進行親核取代反應接上丙炔基,並針對產物進行一系列鑑定與分析,最後將產物與商用benzoxazine (P-d)進行共聚,並針對其固化物性質進行一系列討論,由結果顯示具有丙炔基的benzoxazine固化物,具有優異的熱性質,這是由於其固化物具有較高的交聯密度所致。 綜合來說,本研究以新穎的合成方式,製備一系列磷系benzoxazine與衍生物,其固化物的性質均擁有優異的熱穩定性與難燃特性,具有工業應用的價值。

English Abstract

In this research, we synthesized many phosphorus-containing benzoxazines derived from some typical aromatic amines, such as p-Toluidine, 4-aminophenol, 4-aminobenzoic acid, 4, 4’-diamino diphenyl methane, 4,4’-diaminodiphenyl sulfone , and 4,4’-diaminodiphenyl ether. The thermal properties and the structure-property relationship of the resulting copolymers were studied as follows. First of all, three benzoxazines (I7-I9) with a tolyl, p-hydroxyphenyl or p-carboxyphenyl structure, respectively, were successfully synthesized by a three-pot or two-pot procedure. In the three-pot approach, the first step is the condensation of 2-hydroxybenzaldehyde with p-toluidine, 4-aminophenol and 4-aminobenzoic acid, respectively, forming intermediates (I1-I3) with an imine linkage. The second step is the addition of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) on the imine linkage, resulting in intermediates (I4-I6) with a secondary amine linkage. The last step is the ring closure condensation of (I4-I6), leading to benzoxazines (I7-I9). In the simplified two-pot approach, the first two steps-the condensation and imine reduction were carried out in one reactor, so the yield of (I4-I6) was increased. The structures of monomers (I1-I9) were characterized and confirmed by 1D and 2D NMR spectra. The synthesized benzoxazines were thermally self-cured or copolymerized with a commercial benzoxazine, bis(3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazin-6- yl)methane (F-a). IR analysis was utilized to monitor the ring-opening reaction of (I7-I9) and to propose the structures of P(I7-I9). The microstructure and the structure-property relationship of the resulting homopolymers and copolymers are studied. Secondly, a series of advanced epoxy resins (II2) were prepared by the nucleophilic addition of cresol novolac epoxy (CNE) with a benzoxazine monomer (II1), which is prepared by a one-pot procedure using 2-hydroxybenzaldehyde, 4-aminophenol and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) as starting materials. The nucleophilic addition was monitored by epoxy equivalent weight titration and NMR analysis. Based on this approach, the overall number of functionality of the resulting epoxy resins was retained because a curable benzoxazine linkage was also incorporated after the nucleophilic addition. As a result, high-Tg thermosets qualified for the UL-94 V-0 rating can be achieved after curing. When an UL-94 V-0 rating was achieved, Tg as high as 245 oC (DMA data) was obtained for 4, 4’-diaminediphenyl sulfone (DDS)-cured systems. The corresponding phosphorus content for the UL-94 V-0 rating was as low as 0.61 wt%. The flame retardant nature of oxazine linkage and nitrogen-phosphorus synergistic effect might be responsible for the low phosphorus content required for flame retardancy. Thirdly, three aromatic diamine-based, phosphinated benzoxazines (III7-III9) were prepared from three typical aromatic diamines – 4,4’-diamino diphenyl methane (III1), 4,4’-diamino diphenyl sulfone (III2), and 4,4’-diamino diphenyl ether (III3) by a one-pot procedure. To clarify the reaction mechanism, a two-pot procedure was applied, in which the reaction intermediates (III4-III6) were isolated for characterization. The structures of intermediates and benzoxazines were confirmed by high resolution mass, IR, and 1D and 2D-NMR spectra. In addition to self-polymerization, (III7-III9) were copolymerized with cresol novolac epoxy (CNE). After curing, the homopolymers of P(III7-III9) are brittle while the copolymers of (III7-III9)/CNE are tough. Dynamic mechanical analysis DMA shows the Tgs of (III7-III9)/CNE copolymers are 187, 190 and 171 oC, respectively. Thermal mechanical analysis TMA shows the CTEs of (III7-III9)/CNE copolymers are 46, 38 and 46 ppm, respectively. All the (III7-III9)/CNE copolymers belong to an UL-94 V-0 grade, demonstrating good flame reatardancy. Fourthly, we revealed a facile, one-pot procedure to prepare phosphinated biphenols (IV4-IV6) from the nucleophilic addition of DOPO and aromatic diamine-based benzoxazines. Then, phosphinated biphenols (IV4-IV5) were chosen to prepare two series of advanced epoxy resins (IV7-IV8). After curing (IV7-IV8) with diaminodiphenyl sulfone and phenol novolac, the properties such as glass transition temperature, coefficient of thermal expansion, thermal decomposition temperature, water absorption and flame retardancy of the resulting thermosets were evaluated. The structure-property relationship was also discussed. The resulting epoxy thermosets display moderate to high Tg, good flame retardancy, high modulus, and very low water absorption. Fifthly, we revealed a propargyl ether-containing benzoxazines (V2) from the nucleophilic substitution of a phenolic OH containing benzoxazine (V1) and propargyl bromide in the catalysis of potassium carbonate. The structure of (V2) was characterized and confirmed by high resolution mass spectrum, 1H, 13C, 1H-1H, 1H-13C NMR spectra, and X-ray single crystal diffratogram. IR and DSC were utilized to monitor the ring-opening of oxazine and crosslinking of propargyl ether. The microstructure and the structure-property relationship of the resulting homopolymers and copolymers are discussed. Tg of (V2)-based thermoset, P(V2), is 208 oC by DMA, Coefficient of thermal expansion is 44 ppm/oC, Td 5% is 370 oC. These values are higher than those of (V1)-based thermoset, demonstrating the beneficial effect of crosslinking afforded by the incorporation of propargyl ether group is higher than phenolic OH group. In summary, new mono-functional benzoxazines with a p-hydroxyphenyl, p-carboxyphenyl and propargyl ether linkage, and diamine-based phosphinated benzoxazines or biphenols with electron-withdrawing/donating character, respectively, were successfully prepared by extending Ulrich and Franck’s approach. According to DSC thermograms and IR analysis, the phosphinated benzoxazines can be thermally polymerized. Depending on the structure, moderate to high Tgs can be achieved. In addition to self-curing, phosphinated benzoxazines were also applied as curing agents of cresol novolac epoxy, and the reaction sequence can be monitored by IR analysis. After curing, homogeneous and tough copolymers with good flame retardancy can be achieved.

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