低介电性双环戊二烯型苯并口恶嗪的合成及性能
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摘要
以双环戊二烯、苯酚为原料通过傅克烷基化反应合成双环戊二烯型酚醛单体(DCPDNO),再用所得的DCPDNO与多聚甲醛、苯胺反应合成双环戊二烯型苯并口恶嗪(DCPD-BOZ)。将所得DCPD-BOZ进行高温固化,DCPD-BOZ与环氧树脂E-51进行熔融共混后经过高温固化。采用傅里叶变换红外光谱、核磁共振(~1H-NMR、~(13)C-NMR)等分析了合成产物的化学结构,证明了产物为目标产物;采用差示扫描量热分析对DCPD-BOZ和DCPD-BOZ/E-51共混物的固化特性进行研究;采用热重分析表征了双环戊二烯型聚苯并口恶嗪poly(DCPD-BOZ)和DCPD-BOZ/E-51共混固化物的热稳定性;测试其介电性。结果表明,DCPD-BOZ在207℃出现了固化峰;在N_2的条件下,poly(DCPD-BOZ)失重5%时温度为301℃,在390℃时热分解速率最快,在800℃的残炭率为35%。在室温下介电常数为2.96,介电损耗为0.019。DCPD-BOZ/E-51共混物在240℃产生热效应;在N_2的条件下,DCPD-BOZ/E-51共混物固化物失重5%时温度为357℃,比poly(DCPD-BOZ)提高了56℃。
Dicyclopentadiene-based phenolic monomer(DCPDNO) was synthesized by Friedel-Crafts reaction using dicyclopentadiene and phenol as raw material. The resulting DCPDNO was reacted with paraformaldehyde and aniline to synthesize dicyclopentadiene-based benzoxazine(DCPD-BOZ). The obtained DCPD-BOZ was mixed with epoxy resin,and then cured at high temperature. The chemical structure of the synthesized product was analyzed by FT-IR, ~1H-NMR, ~(13)C-NMR and the like, and the product was proved to be the target product. The curing properties of DCPD-BOZ and DCPD-BOZ/E-51 blends were studied by DSC. the thermal stability of dicyclopentadiene-based benzoxazine poly(DCPD-BOZ) and cured DCPD-BOZ/E-51 blends was studied by TGA,with testing its dielectric property. The results show that DCPD-BOZ has a curing peak at 207 ℃. Under N_2 condition, poly(DCPD-BOZ) has the 5% mass loss temperature of 305 ℃, and has the fastest thermal decomposition rate at 390 ℃. The residual carbon rate at 800 ℃ is 35%. Its dielectric constant of room temperature is 2.96,and dissipation factor is 0.019.The DCPD-BOZ/E-51 blends show a reaction peak at 240 ℃ and the DCPD-BOZ/E-51 blends have a mass loss temperature of 357 ℃ under 5%, increased by 56 ℃.
Dicyclopentadiene-based phenolic monomer(DCPDNO) was synthesized by Friedel-Crafts reaction using dicyclopentadiene and phenol as raw material. The resulting DCPDNO was reacted with paraformaldehyde and aniline to synthesize dicyclopentadiene-based benzoxazine(DCPD-BOZ). The obtained DCPD-BOZ was mixed with epoxy resin,and then cured at high temperature. The chemical structure of the synthesized product was analyzed by FT-IR, ~1H-NMR, ~(13)C-NMR and the like, and the product was proved to be the target product. The curing properties of DCPD-BOZ and DCPD-BOZ/E-51 blends were studied by DSC. the thermal stability of dicyclopentadiene-based benzoxazine poly(DCPD-BOZ) and cured DCPD-BOZ/E-51 blends was studied by TGA,with testing its dielectric property. The results show that DCPD-BOZ has a curing peak at 207 ℃. Under N_2 condition, poly(DCPD-BOZ) has the 5% mass loss temperature of 305 ℃, and has the fastest thermal decomposition rate at 390 ℃. The residual carbon rate at 800 ℃ is 35%. Its dielectric constant of room temperature is 2.96,and dissipation factor is 0.019.The DCPD-BOZ/E-51 blends show a reaction peak at 240 ℃ and the DCPD-BOZ/E-51 blends have a mass loss temperature of 357 ℃ under 5%, increased by 56 ℃.
引文
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[13] Wang Y X,Ishida H. Synthesis and properties of new thermoplastic polymers from substituted 3, 4-dihydro-2 H-1, 3-benzoxazines[J].Macromolecules, 2000, 33: 2839-2847.
[14] Liu Y L, Yu J M, Chou C I. Preparation and properties of novel benzoxazine and polybenzoxazine with maleimide groups[J].J. Polym. Sci. Part A: Polym. Chem., 2004 , 42: 5954-5963.
[15] Ishida H, Rodriguez Y. Curing kinetics of a new benzoxazine-based phenolic resin by differential scanning calorimetry[J].Polymer, 1995, 36: 3151-3158.
[16] Hougham G, Tesoro G, Shaw J. The synthesis and properties of polyimides made from perfluoro aromatic diamines[C]//Abstracts of Papers of the American Chemical Society. Washington DC: American Chemical Society, 1989, 198: 79-PMSE.
[2] Agag T, Takeichi T. Novel benzoxazine monomers containing p-phenyl propargyl ether: polymerization of monomers and properties of polybenzoxazines [J]. Macromolecules , 2001, 34: 7257-7263.
[3] 袁伟, 史铁钧, 徐国梅, 等. 含双马来酰亚胺的新型双苯并口恶嗪的合成及性能[J]. 化工学报, 2016, 67(5): 2131-2137.Yuan W,Shi T J,Xu G M,et al. Fabrication and characterization of a novel bismaleimide-benzoxazine resin [J]. Journal of Chemical Industry, 2016, 67(5): 2131-2137.
[4] Shen S B, Ishida H. Synthesis and characterization of polyfunctional naphthoxazines and related polymers [J].J. Appl. Polym. Sci., 1996, 61: 1595-1605.
[5] Hsiue G H, Shiao S J, Wei H F, et al. Novel phosphorus-containing dicyclopentadiene‐modified phenolic resins for flame-retardancy applications[J]. J. Appl. Polym. Sci., 2001, 79: 342-349.
[6] Agag T, Jin L, Ishida H. A new synthetic approach for difficult benzoxazines: preparation and polymerization of 4, 4′-diaminodiphenyl sulfone-based benzoxazine monomer[J].Polymer, 2009, 50: 5940-5944.
[7] Cheng Y, Yang J, Jin Y, et al. Synthesis and properties of highly cross-linked thermosetting resins of benzocyclobutene-functionalized benzoxazine[J].Macromolecules, 2012, 45: 4085-4091.
[8] Chernykh A, Agag T, Ishida H. Effect of polymerizing diacetylene groups on the lowering of polymerization temperature of benzoxazine groups in the highly thermally stable, main-chain-type polybenzoxazines[J].Macromolecules, 2009, 42: 5121-5127.
[9] Konno H, Shiba K, Kaburagi Y,et al. Carbonization and graphitization of Kapton-type polyimide film having boron-bearing functional groups [J]. Carbon, 2001, 39: 1731-1740.
[10] Ishida H, Allen D J. Mechanical characterization of copolymers based on benzoxazine and epoxy[J]. Polymer, 1996, 37: 4487-4495.
[11] Ishida H, Lee Y H. Infrared and thermal analyses of polybenzoxazine and polycarbonate blends[J]. J. Appl. Polym. Sci., 2001, 81: 1021-1034.
[12] Li Y L, Tang B M, Liang Z Q, et al. Study on the curing process of benzoxazine-epoxy copolymerization [J]. Thermosetting Resin, 2008, 2: 005.
[13] Wang Y X,Ishida H. Synthesis and properties of new thermoplastic polymers from substituted 3, 4-dihydro-2 H-1, 3-benzoxazines[J].Macromolecules, 2000, 33: 2839-2847.
[14] Liu Y L, Yu J M, Chou C I. Preparation and properties of novel benzoxazine and polybenzoxazine with maleimide groups[J].J. Polym. Sci. Part A: Polym. Chem., 2004 , 42: 5954-5963.
[15] Ishida H, Rodriguez Y. Curing kinetics of a new benzoxazine-based phenolic resin by differential scanning calorimetry[J].Polymer, 1995, 36: 3151-3158.
[16] Hougham G, Tesoro G, Shaw J. The synthesis and properties of polyimides made from perfluoro aromatic diamines[C]//Abstracts of Papers of the American Chemical Society. Washington DC: American Chemical Society, 1989, 198: 79-PMSE.