一种新型芳香—脂肪不对称二胺及含吡啶脂环结构二胺的聚酰亚胺材料研究
发布时间：2018-07-24 19:32
【摘要】：随着微电子,柔性显示及光伏产业的发展,聚酰亚胺的发展也迎来了又一个春天。传统芳香聚酰亚胺(PIs)凭借优异的热性能和机械性能而得到广泛应用。但是在一些新兴行业,对其要求不只是局限于良好的热性能和机械性能。在微电子产业,要求聚酰亚胺具有较低的介电常数,而在柔性显示(OLED)行业,则对聚酰亚胺的光学透过性提出了更高的要求。因此就要对传统的芳香聚酰亚胺进行各种改性研究从而使其可以应用于不同的领域。根据以往的研究,在聚酰亚胺主链中,不对称结构的引入可以有效的减少分子间的紧密堆积,破坏分子的规整性;脂肪链,醚键可以提高分子链的柔性,脂肪链可以破坏分子间的共轭,有效的减弱CT效应;分子间产生的交联和氢键结构可以有效限制分子链的运动,提高材料的热性能;吡啶杂环与苯环具有类似的结构与性质,但是,由于吡啶杂环中-C-N=C-键(4.10)比苯环中-C=C-键(1.76)具有更高的摩尔折射率,使其可以有效的增加材料的光学透过性,同时吡啶杂环的引入还可以使PIs热稳定性再次提高,吡啶杂环结构可以阻碍分子间的相互作用,增加分子链间距。首先,我们用简单易得的对羟基苯甲醛为原料与2-氯-5-硝基吡啶发生亲核取代反应,合成出4-(5-硝基吡啶氧基)苯甲醛(NPyOBH),然后以NPyOBH为底物与硝基甲烷发生Henry反应合成出β-[4-(5-硝基吡啶氧基)苯基]硝基乙醇(NPyOPhNE)。NPyOPhNE还原之后即得到二胺2-胺基-1-[4-(5-氨基吡啶氧基)苯基]-1-乙醇(AAPyPhE)。将AAPyPhE以不同的比例掺杂到ODA中,然后分别与ODPA,6FDA,BPDA,BTDA通过传统的两步法聚合得到PIs薄膜。对薄膜材料进行表征,结果显示,当掺杂AAPyPh E后薄膜材料的溶解性得到提高,对于OPI-x体系,紫外截止波长在365~381 nm之间,T500透过率在74.1~83.3%范围内。XRD测试出分子间平均间距4.7~5.1?之间。由于AAPyPhE可以在分子链之间形成交联结构和分子间氢键,所以当AAPyPhE的含量在某一值以下时,材料仍然维持原有的良好的热力学与机械性能,拉力测试结果显示材料的拉伸强度为89.35~170.73 MPa之间,断裂伸长率范围在8.43~10.82%之间,弹性模量在1.29~2.28 GPa之间。随着AAPyPh E含量的增加其Tg逐渐减小,范围在185.5~253.3 oC之间,5%分解温度范围为338.7~498.3 oC,10%热分解温度为391.6~545.5 oC之间,且残余量在49.1~56.6%之间。但是由于众多结构因素的影响,随着AAPyPh E的加入材料的介电性能也有了改变。介电测试表明5%mol含量的AAPyPhE可以使介电常数ε?降低,但是随着AAPyPh E继续加入后,ε?值将出现起伏变化。其次,利用实验室已合成出的含cardo脂环结构的吡啶杂环二胺1,1-双[4-(-氨基吡啶氧基)苯基]环己烷(BAPBH)分别与ODPA,6FDA,BPDA,BTDA通过传统的两步法聚合得到PIs薄膜,并对PIs薄膜进行表征,由于吡啶杂环的引入,材料的热性能优异,光学性能也较好。同时脂环结构破坏了分子链的紧密堆积,减小了分子的结晶度,使材料的加工性能提高。PIs的介电常数也相对较低。最后,以先前合成的NPyOBH为原料,通过与TMSCF3或者KBH4反应得到相应的醇类:1-三氟甲基-1-[4-(5-硝基吡啶氧基)苯基]甲醇(FNPyOPh MA)和4-(5-硝基吡啶氧基)苯甲醇(NPyOPhCA),然后再与对硝基苯甲酰氯合成出不对称结构的二硝基,1-三氟甲基-1-[4-(5-硝基吡啶氧基)苯基]甲基-4-硝基苯甲酸酯(FNPyOPh MNBZ)和4-(5-硝基吡啶氧基)苄基-4-硝基苯甲酸酯(NPyOBNBZ)。FNPyOPhMNBZ和NPyOBNBZ经过Pd/C水合肼氢化还原,制备相应的二胺1-三氟甲基-1-[4-(5-氨基吡啶氧基)苯基]甲基-4-氨基苯甲酸酯(FAPyOPhMABZ)和4-(5-氨基吡啶氧基)苄基-4-氨基苯甲酸酯(APyOBABZ)。由红外和核磁表征确定结构。
[Abstract]:With the development of microelectronics, flexible display and photovoltaic industry, the development of polyimide also ushered in another spring. The traditional aromatic polyimide (PIs) has been widely used for its excellent thermal and mechanical properties. However, in some emerging industries, it is not confined to good thermal and mechanical properties. The industry requires polyimide with a lower dielectric constant and a higher requirement for the optical transmittance of polyimides in the flexible display (OLED) industry. The introduction of asymmetric structure can effectively reduce the close accumulation of molecules and destroy the regularity of molecules. Fat chains and ether bonds can improve the flexibility of molecular chains. The fat chains can destroy the conjugation between molecules and effectively weaken the CT effect. Intermolecular crosslinking and hydrogen bonded structures can effectively restrict the movement of molecular chains and improve materials. Pyridine heterocyclic rings have similar structures and properties, but because the -C-N=C- bond (4.10) in the pyridine heterocycle has a higher molar refractive index than the -C=C- bond in the benzene ring (1.76), the pyridine heterocycle can effectively increase the optical transmittance of the material. At the same time, the introduction of pyridine heterocyclic ring can also improve the thermal stability of the PIs, and the pyridine heterocyclic junction. Structure can impede intermolecular interaction and increase the distance between molecular chains. First, we use a simple and easy nucleophilic substitution reaction of 2- chloro -5- nitropyridine to synthesize 4- (5- nitropyridyl) benzaldehyde (NPyOBH), and then synthesize beta -[4- (5- nitro) by Henry reaction with NPyOBH as substrate and nitromethane. Two amines 2- amino group -1-[4- (5- amino pyridyl) phenyl]-1- ethanol (AAPyPhE) was obtained after the reduction of pyridyl phenyl] nitro ethanol (NPyOPhNE).NPyOPhNE. AAPyPhE was doped into ODA in a different proportion, and then ODPA, 6FDA, BPDA, respectively. The film was obtained by the traditional two step polymerization. It is shown that the solubility of the film material is improved when the AAPyPh E is doped. For the OPI-x system, the UV cut-off wavelength is between 365~381 nm and the T500 transmittance is measured between the average intermolecular distance 4.7~5.1 within the 74.1~83.3% range. Because AAPyPhE can form the joint structure and the intermolecular hydrogen bond between the molecular chains, so when AAPyPhE When the content is below a certain value, the material still maintains the original good thermodynamic and mechanical properties. The tensile test results show that the tensile strength of the material is 89.35~170.73 MPa, the elongation at break range is between 8.43~10.82% and the modulus of elasticity is between 1.29~2.28 GPa. With the increase of AAPyPh E content, the Tg gradually decreases, the range is in 185.5~. Between 253.3 oC, the 5% decomposition temperature range is 338.7~498.3 oC, the 10% thermal decomposition temperature is 391.6~545.5 oC, and the residual amount is between 49.1~56.6%. However, the dielectric properties of the material with the addition of AAPyPh E are also changed due to the influence of many structural factors. The dielectric test shows that the AAPyPhE of 5% mol content can reduce the dielectric constant. But with the continuous addition of AAPyPh E, the value of the epsilon will fluctuate. Secondly, the PIs film is synthesized by the two step method of ODPA, 6FDA, BPDA, BTDA, respectively, by the two step method of ODPA, 6FDA, BPDA, BTDA, which have been synthesized by the laboratory, which contains the cardo liporing structure of the pyridine heterocyclic cyclohexane (BAPBH), respectively, and characterize the PIs film. Due to the introduction of pyridine heterocyclic ring, the thermal properties of the materials are excellent and the optical properties are better. At the same time, the ring structure destroys the close accumulation of the molecular chain, reduces the crystallinity of the molecules, and makes the material processing properties increase the dielectric constant of.PIs relatively low. Finally, the previously synthesized NPyOBH is used as the raw material to react with TMSCF3 or KBH4. The corresponding alcohols: 1- three fluoromethyl -1-[4- (5- nitropyridoxy) phenyl] methanol (FNPyOPh MA) and 4- (5- nitropyridyl) benzyl alcohol (NPyOPhCA), and then synthesis of the asymmetric structure of two nitro, 1- three fluoromethyl -1-[4- (5- nitropyridoxy) methyl -4- Nitrobenzoic Acid Ester Benzyl -4- nitrobenzoate (NPyOBNBZ).FNPyOPhMNBZ and NPyOBNBZ were hydrogenated by hydrazine hydrate of Pd/C, and the corresponding two amine 1- three fluoromethyl -1-[4- (5- amino pyridoxy) phenyl] methyl -4- amino benzoate (FAPyOPhMABZ) and 4- (5- amino pyridyl) benzyl amino benzoate ester were prepared. NMR characterization determines the structure.
【学位授予单位】：南昌大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O633.2
本文编号：2142428
[Abstract]:With the development of microelectronics, flexible display and photovoltaic industry, the development of polyimide also ushered in another spring. The traditional aromatic polyimide (PIs) has been widely used for its excellent thermal and mechanical properties. However, in some emerging industries, it is not confined to good thermal and mechanical properties. The industry requires polyimide with a lower dielectric constant and a higher requirement for the optical transmittance of polyimides in the flexible display (OLED) industry. The introduction of asymmetric structure can effectively reduce the close accumulation of molecules and destroy the regularity of molecules. Fat chains and ether bonds can improve the flexibility of molecular chains. The fat chains can destroy the conjugation between molecules and effectively weaken the CT effect. Intermolecular crosslinking and hydrogen bonded structures can effectively restrict the movement of molecular chains and improve materials. Pyridine heterocyclic rings have similar structures and properties, but because the -C-N=C- bond (4.10) in the pyridine heterocycle has a higher molar refractive index than the -C=C- bond in the benzene ring (1.76), the pyridine heterocycle can effectively increase the optical transmittance of the material. At the same time, the introduction of pyridine heterocyclic ring can also improve the thermal stability of the PIs, and the pyridine heterocyclic junction. Structure can impede intermolecular interaction and increase the distance between molecular chains. First, we use a simple and easy nucleophilic substitution reaction of 2- chloro -5- nitropyridine to synthesize 4- (5- nitropyridyl) benzaldehyde (NPyOBH), and then synthesize beta -[4- (5- nitro) by Henry reaction with NPyOBH as substrate and nitromethane. Two amines 2- amino group -1-[4- (5- amino pyridyl) phenyl]-1- ethanol (AAPyPhE) was obtained after the reduction of pyridyl phenyl] nitro ethanol (NPyOPhNE).NPyOPhNE. AAPyPhE was doped into ODA in a different proportion, and then ODPA, 6FDA, BPDA, respectively. The film was obtained by the traditional two step polymerization. It is shown that the solubility of the film material is improved when the AAPyPh E is doped. For the OPI-x system, the UV cut-off wavelength is between 365~381 nm and the T500 transmittance is measured between the average intermolecular distance 4.7~5.1 within the 74.1~83.3% range. Because AAPyPhE can form the joint structure and the intermolecular hydrogen bond between the molecular chains, so when AAPyPhE When the content is below a certain value, the material still maintains the original good thermodynamic and mechanical properties. The tensile test results show that the tensile strength of the material is 89.35~170.73 MPa, the elongation at break range is between 8.43~10.82% and the modulus of elasticity is between 1.29~2.28 GPa. With the increase of AAPyPh E content, the Tg gradually decreases, the range is in 185.5~. Between 253.3 oC, the 5% decomposition temperature range is 338.7~498.3 oC, the 10% thermal decomposition temperature is 391.6~545.5 oC, and the residual amount is between 49.1~56.6%. However, the dielectric properties of the material with the addition of AAPyPh E are also changed due to the influence of many structural factors. The dielectric test shows that the AAPyPhE of 5% mol content can reduce the dielectric constant. But with the continuous addition of AAPyPh E, the value of the epsilon will fluctuate. Secondly, the PIs film is synthesized by the two step method of ODPA, 6FDA, BPDA, BTDA, respectively, by the two step method of ODPA, 6FDA, BPDA, BTDA, which have been synthesized by the laboratory, which contains the cardo liporing structure of the pyridine heterocyclic cyclohexane (BAPBH), respectively, and characterize the PIs film. Due to the introduction of pyridine heterocyclic ring, the thermal properties of the materials are excellent and the optical properties are better. At the same time, the ring structure destroys the close accumulation of the molecular chain, reduces the crystallinity of the molecules, and makes the material processing properties increase the dielectric constant of.PIs relatively low. Finally, the previously synthesized NPyOBH is used as the raw material to react with TMSCF3 or KBH4. The corresponding alcohols: 1- three fluoromethyl -1-[4- (5- nitropyridoxy) phenyl] methanol (FNPyOPh MA) and 4- (5- nitropyridyl) benzyl alcohol (NPyOPhCA), and then synthesis of the asymmetric structure of two nitro, 1- three fluoromethyl -1-[4- (5- nitropyridoxy) methyl -4- Nitrobenzoic Acid Ester Benzyl -4- nitrobenzoate (NPyOBNBZ).FNPyOPhMNBZ and NPyOBNBZ were hydrogenated by hydrazine hydrate of Pd/C, and the corresponding two amine 1- three fluoromethyl -1-[4- (5- amino pyridoxy) phenyl] methyl -4- amino benzoate (FAPyOPhMABZ) and 4- (5- amino pyridyl) benzyl amino benzoate ester were prepared. NMR characterization determines the structure.
【学位授予单位】：南昌大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O633.2
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