一種新型芳香—脂肪不對(duì)稱二胺及含吡啶脂環(huán)結(jié)構(gòu)二胺的聚酰亞胺材料研究
發(fā)布時(shí)間：2018-07-24 19:32
【摘要】：隨著微電子,柔性顯示及光伏產(chǎn)業(yè)的發(fā)展,聚酰亞胺的發(fā)展也迎來(lái)了又一個(gè)春天。傳統(tǒng)芳香聚酰亞胺(PIs)憑借優(yōu)異的熱性能和機(jī)械性能而得到廣泛應(yīng)用。但是在一些新興行業(yè),對(duì)其要求不只是局限于良好的熱性能和機(jī)械性能。在微電子產(chǎn)業(yè),要求聚酰亞胺具有較低的介電常數(shù),而在柔性顯示(OLED)行業(yè),則對(duì)聚酰亞胺的光學(xué)透過(guò)性提出了更高的要求。因此就要對(duì)傳統(tǒng)的芳香聚酰亞胺進(jìn)行各種改性研究從而使其可以應(yīng)用于不同的領(lǐng)域。根據(jù)以往的研究,在聚酰亞胺主鏈中,不對(duì)稱結(jié)構(gòu)的引入可以有效的減少分子間的緊密堆積,破壞分子的規(guī)整性;脂肪鏈,醚鍵可以提高分子鏈的柔性,脂肪鏈可以破壞分子間的共軛,有效的減弱CT效應(yīng);分子間產(chǎn)生的交聯(lián)和氫鍵結(jié)構(gòu)可以有效限制分子鏈的運(yùn)動(dòng),提高材料的熱性能;吡啶雜環(huán)與苯環(huán)具有類似的結(jié)構(gòu)與性質(zhì),但是,由于吡啶雜環(huán)中-C-N=C-鍵(4.10)比苯環(huán)中-C=C-鍵(1.76)具有更高的摩爾折射率,使其可以有效的增加材料的光學(xué)透過(guò)性,同時(shí)吡啶雜環(huán)的引入還可以使PIs熱穩(wěn)定性再次提高,吡啶雜環(huán)結(jié)構(gòu)可以阻礙分子間的相互作用,增加分子鏈間距。首先,我們用簡(jiǎn)單易得的對(duì)羥基苯甲醛為原料與2-氯-5-硝基吡啶發(fā)生親核取代反應(yīng),合成出4-(5-硝基吡啶氧基)苯甲醛(NPyOBH),然后以NPyOBH為底物與硝基甲烷發(fā)生Henry反應(yīng)合成出β-[4-(5-硝基吡啶氧基)苯基]硝基乙醇(NPyOPhNE)。NPyOPhNE還原之后即得到二胺2-胺基-1-[4-(5-氨基吡啶氧基)苯基]-1-乙醇(AAPyPhE)。將AAPyPhE以不同的比例摻雜到ODA中,然后分別與ODPA,6FDA,BPDA,BTDA通過(guò)傳統(tǒng)的兩步法聚合得到PIs薄膜。對(duì)薄膜材料進(jìn)行表征,結(jié)果顯示,當(dāng)摻雜AAPyPh E后薄膜材料的溶解性得到提高,對(duì)于OPI-x體系,紫外截止波長(zhǎng)在365~381 nm之間,T500透過(guò)率在74.1~83.3%范圍內(nèi)。XRD測(cè)試出分子間平均間距4.7~5.1?之間。由于AAPyPhE可以在分子鏈之間形成交聯(lián)結(jié)構(gòu)和分子間氫鍵,所以當(dāng)AAPyPhE的含量在某一值以下時(shí),材料仍然維持原有的良好的熱力學(xué)與機(jī)械性能,拉力測(cè)試結(jié)果顯示材料的拉伸強(qiáng)度為89.35~170.73 MPa之間,斷裂伸長(zhǎng)率范圍在8.43~10.82%之間,彈性模量在1.29~2.28 GPa之間。隨著AAPyPh E含量的增加其Tg逐漸減小,范圍在185.5~253.3 oC之間,5%分解溫度范圍為338.7~498.3 oC,10%熱分解溫度為391.6~545.5 oC之間,且殘余量在49.1~56.6%之間。但是由于眾多結(jié)構(gòu)因素的影響,隨著AAPyPh E的加入材料的介電性能也有了改變。介電測(cè)試表明5%mol含量的AAPyPhE可以使介電常數(shù)ε?降低,但是隨著AAPyPh E繼續(xù)加入后,ε?值將出現(xiàn)起伏變化。其次,利用實(shí)驗(yàn)室已合成出的含cardo脂環(huán)結(jié)構(gòu)的吡啶雜環(huán)二胺1,1-雙[4-(-氨基吡啶氧基)苯基]環(huán)己烷(BAPBH)分別與ODPA,6FDA,BPDA,BTDA通過(guò)傳統(tǒng)的兩步法聚合得到PIs薄膜,并對(duì)PIs薄膜進(jìn)行表征,由于吡啶雜環(huán)的引入,材料的熱性能優(yōu)異,光學(xué)性能也較好。同時(shí)脂環(huán)結(jié)構(gòu)破壞了分子鏈的緊密堆積,減小了分子的結(jié)晶度,使材料的加工性能提高。PIs的介電常數(shù)也相對(duì)較低。最后,以先前合成的NPyOBH為原料,通過(guò)與TMSCF3或者KBH4反應(yīng)得到相應(yīng)的醇類: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),然后再與對(duì)硝基苯甲酰氯合成出不對(duì)稱結(jié)構(gòu)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)芐基-4-硝基苯甲酸酯(NPyOBNBZ)。FNPyOPhMNBZ和NPyOBNBZ經(jīng)過(guò)Pd/C水合肼氫化還原,制備相應(yīng)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)芐基-4-氨基苯甲酸酯(APyOBABZ)。由紅外和核磁表征確定結(jié)構(gòu)。
[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.
【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
本文編號(hào)：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.
【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
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