浅色可溶含氟聚酰亚胺的合成与性能研究

利用含氟二胺2,2一双[4-(4-氨基-2-三氟甲基苯氧基)苯基]六氟丙烷分别与1,2,3,4-环丁烷四酸二酐、均苯四甲酸二酐、3,3,,4,4'-联苯四酸二酐、3,3',4,4'-二苯醚四酸二酐和3,3',4,4'-二苯酮四酸二酐进行低温缩聚反应,经热酰亚胺化制备出5种含氟聚酰亚胺(PI)薄膜,均表现出优良的综合性能.其中,含脂环PI薄膜在可见光波长范围内(400～700nm)具有优异的光学透明性,450nm处的透光率为84.6%,紫外截止波长为307.2nm,近乎无色透明,且5种含氟PI在光通讯波段(1.30μm和1.55μm)无明显吸收;这些含氟PI均具有良好的溶解性;除含脂环PI的热稳定性稍差外,4种芳香PI薄膜的5%热失重温度均超过519℃,具有良好的热稳定性.     

包装纸中丙烯酰胺及芳香胺迁移量的检测研究

目的建立同时测定包装纸中丙烯酰胺和6种芳香胺迁移量的检测方法。方法通过筛选固相萃取小柱种类,优化净化方法和液相色谱条件,从而形成丙烯酰胺和6种芳香胺迁移量的固相萃取-高效液相色谱检测方法。结果丙烯酰胺在0.2~20 mg/L的浓度范围内线性关系良好(R2=0.9989),检测波长为220 nm,检出限为0.01 mg/L;芳香胺在0.2~20 mg/L的浓度范围内线性关系良好(R20.998),检测波长为240和280 nm,检出限也为0.01 mg/L。纯水样品中,各化合物的加标回收率在90%以上,相对标准偏差为2.3%~5.9%。实际样品中,芳香胺的加标回收率在86.9%以上,相对标准偏差为2.0%~6.1%;丙烯酰胺的加标回收率为78.7%~81.9%,相对标准偏差为4.2%~6.2%。结论该方法处理步骤简单,分离效果好,精密度高,从提高检测效率、节约成本的角度来看,该方法值得推广成为常规检测方法。     

含螺环结构的二胺及其聚酰亚胺的合成与性能

首先,以双酚A和甲磺酸反应合成出3,3,3',3'-四甲基-6,6'-二羟基-1,1'-螺旋双茚满,然后与2-氯-5-硝基三氟甲苯反应得到3,3,3',3'-四甲基-6,6'-双[4-硝基-2-三氟甲基苯氧基]-1,1'-螺旋双茚满,最后在Pd/C-水合肼还原作用下得到3,3,3',3'-四甲基-6,6'-双[4-氨基-2-三氟甲基苯氧基]-1,1'-螺旋双茚满。采用上述二胺单体分别与1,2,3,4-环丁烷四酸二酐、均苯四甲酸二酐、联苯二酐、3,3',4,4'-二苯醚四酸二酐、3,3',4,4'-二苯酮四酸二酐和六氟二酐通过两步法制备出6种含螺环结构的聚酰亚胺(PI)。采用核磁、红外光谱、X射线衍射、紫外-可见光谱、热重分析、差示扫描量热分析和溶解性测试等手段表征了所得化合物和PI的结构与性能。研究结果表明,这些含螺环的PI主要表现为非晶结构和较大的分子链间距离,且具有良好的溶解性、光学性能和热性能。     

含异丙基和联苯结构可溶性聚酰胺的合成与表征

一种新型含异丙基和大侧基联苯结构二胺单体3,3'-二异丙基-4,4'-二氨基苯基-4″-苯基甲苯(PAPT),与3种二酐通过Yamazaki膦酰化法缩聚制得3种聚芳酰胺薄膜。研究表明,聚合物具有良好的溶解性能,常温下能溶于N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、N,N-二甲基乙酰胺(DMAc)等溶剂;具有突出的热性能,玻璃化转变温度均高于209℃,氮气氛围下10%热失重温度高于465℃;光学性能优良,截止波长范围在317~338nm,透过率超过80%的波长都大于445 nm。     

液相色谱法测定食品包装用油墨中11种光引发剂的含量

目的 建立油墨中光引发剂的检测方法，从源头控制食品包装的安全。方法 油墨样品经乙酸乙酯和乙腈超声提取，体积分数为20%的乙腈溶液定容，固相萃取柱萃取后用乙腈定容，使用液相色谱进行测定。结果 11种成分在各自范围内线性关系良好（R≥0.999 5），平均加样回收率为90.0%～95.0%，相对标准偏差（n=6）小于3.5%。结论 建立了液相色谱同时测定油墨中2-甲基-1-(4-甲基硫代苯基)-2-(4-吗啉基)-1-丙酮、1-羟基环己基苯基酮、2-苯甲酰基苯甲酸甲酯、4-二甲氨基苯甲酸乙酯、4,4’-二（N,N-二甲氨基）二苯甲酮、安息香双甲醚、4-甲基二苯甲酮、4,4’-二（N,N-二乙氨基）二苯甲酮、对二甲氨基苯甲酸异辛酯、2-异丙基硫杂蒽酮、2,4-二乙基噻唑酮的方法。     

双马来酰亚胺与4,4'-二氨基二苯醚预聚反应的产物分析

芳香胺改性双马来酰亚胺是双马来酰亚胺最主要的改性方法。本文通过凝胶渗透色谱、酸碱滴定、高效液相色谱等方法分析双马来酰亚胺(BDM)与4,4'-二氨基二苯醚预聚(DDE)的反应物组成,推断产物结构式。结果表明,该条件下的BDM与DDE预聚反应,DDE绝大部分参加反应,BDM则显著剩余。产物中的伯胺主要来自DDE一端的伯胺与双马来酰亚胺的双键加成而另外一端没有加成的生成物。     

一类含双叔丁基苯结构聚酰亚胺的合成与性能

通过分子设计制备一种含双叔丁基结构的刚性芳香二胺单体——4,4′-二氨基苯基-3″,5″-二叔丁基甲苯,将该二胺单体分别与3种不同的商品化芳香二酐(3,3′,4,4′-联苯四酸二酐(BPDA)、3,3′,4,4′-二苯醚酐(ODPA)、3,3′,4,4′-二苯酮四酸二酐(BTDA))采用一步高温缩聚制备了3种新型聚酰亚胺NPI(3a～3c)。该类聚酰亚胺具有优异的溶解成膜性能,在室温可溶解于N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、间甲酚等高沸点溶剂中,在加热时还能溶解于CHCl_3,CH_2Cl_2,THF等低沸点溶剂,并可通过其聚合物溶液浇铸得到柔韧的薄膜;所制聚酰亚胺薄膜具有优良的热性能,玻璃化转变温度(T_g)范围为262～303℃,在N_2中质量损失10%的温度超过523℃;具有优异的光学性能,所制薄膜还具有较浅的颜色和良好的光学透过性,在450 nm波长光下的透光率为69%～76%,截止波长为341～353 nm。     

联苯类三芳胺空穴传输材料的合成及其光电性能研究

以4,4'-二甲基二苯胺和3-甲基二苯胺为原料分别与4,4'-二碘联苯反应合成了N,N,N',N'-四(4-甲基苯基)-1,1'-联苯-4,4'-二胺(S-100)和N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺(m-TPD),产品收率为93.3%和94.3%.以S-100和m-TPD作为空穴传输材料,以酞菁氧钛为电荷产生材料制备功能分离型有机光导器件并进行光电性能的测试,结果表明所合成化合物具有优异的空穴传输性能.     

联苯型三芳胺空穴传输材料的新合成工艺研究

三芳胺是一种优良的空穴传输材料,在有机电致发光和有机光导领域有着重要应用.目前的合成方法是在氯化亚铜和邻菲哆啉的催化下,以4,4'-二-碘联苯和二芳基胺反应制备.研究了以4,4'-二溴联苯与二苯胺为原料,研究了在醋酸钯、三叔丁基膦的催化作用下合成N,N,N’,N’-四苯基-1,1'-联苯-4,4’-二胺(TPD)的反应.考察了原料配比、反应时间、催化剂用量以及反应温度对产品收率的影响,得到优化工艺条件为二苯胺与4,4 '-二溴联苯的摩尔比为2.5∶1,醋酸钯用量为0.05mmol,在145℃回流反应6h,产品收率为78.89％.在此条件下,用4,4’-二溴联苯分别与3-甲基二苯胺、4-甲基二苯胺反应合成了N,N'N'-二苯基-N,N '-二(3-甲基苯基)-1,1'-联苯-4,4’-二胺(m-TPD)、N,N’-二苯基-N,N’-二(4-甲基苯基)-1,1’-联苯-4,4’-二胺(p-TPD),产品收率分别为75.59％和69.96％.通过比较,新工艺有效地降低了工艺物料平衡图(PFD)类空穴传输材料的合成成本.     

6FAPE基含氟聚酰亚胺的结构与性能研究

利用含氟二胺单体4,4'-双(4-氨基-2-三氟甲基苯氧基)二苯醚(6FAPE),分别与1,2,3,4-环丁烷四酸二酐(CBDA)、3,3',4,4'-二苯醚四酸二酐(ODPA)、3,3',4,4'-联苯四酸二酐(BPDA)、3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)和均苯四甲酸二酐(PMDA)进行低温缩聚反应,经热酰亚胺化制备出5种聚酰亚胺(PI)薄膜,考察了其光学透明性和热性能,研究了聚酰亚胺分子结构与性能的关系.结果表明,CBDA基含氟PI薄膜在可见光波长范围内(400～700nm)具有优异的光学透明性,450nm处的透光率为84.6%,且5种含氟PI薄膜在光通讯波段(1.30μm和1.55μm)均无明显吸收;除CBDA外,含氟PI薄膜均具有良好的热稳定性,5%热失重温度超过530℃;5种含氟PT薄膜的玻璃化转变温度Tg均在200℃以上,且CBDA基舍氟PI薄膜的Tg最高,达到265.5℃.     

聚氨酯弹性体的合成和水下声学性能

用甲苯-2,4-二异氰酸酯(2,4-TDI)、聚醚二醇(PPO)和3,3’-二氯-4,4’-二氨基二苯基甲烷(MOCA)等原料合成了聚氨酯弹性体,在脉冲声管中测试了合成试样的声压反射系数和吸声系数,研究了合成工艺参数对其水下声学性能的影响。测试结果表明,TDI-PPO-MOCA合成型聚氨酯弹性体是一种良好的水下吸声材料,其吸声性能受到固化温度,扩链剂含量等参数的影响。加入填料和改变其结构可以进一步改善聚氨酯弹性体的水下声学性能,因此合理地设计实验工艺参数,可以得到水下声学性能更佳的聚氨酯弹性体。为工业生产提供了理论参考。     

Synthesis and characterization of novel,soluble sulfur-containing copolyimides with high refractive indices

High refractive index, colorless polymers with high temperature resistancy are of great industrial interest. In this study, new sulfur-containing copolyimides with high refractive indices have been synthesized via polycondensation reaction using 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA) as dianhydride monomers, and 4,4′-diaminodiphenyl sulfide (4,4′-SDA) and 2,3,5,6-tetramethyl-1,4-phenylene diamine (4MPD) as well as 3,3′-diaminodiphenyl sulfone (3,3′-DDS) as diamino monomers. The resulting copolyimides are amorphous and soluble in common organic solvents such as dimethylacetamide and N-methylpyrrolidone. They also exhibit very good optical properties such as high transparency (>88% at 589.6 nm) for samples with a thickness of 120–150 μm. Furthermore, higher refractive indices ranging from 1.64 to 1.72 at visible wavelengths compared to currently applied polymer materials, which show refractive indices between 1.5 and 1.6, are found. In addition, the copolyimides synthesized in this study show high thermal stability with glass transition temperatures between 273 and 306 °C.     

ODPA/异构ODA共聚酰亚胺的合成及其性能研究

采用3,3′,4,4′-二苯醚四甲酸二酐(3,3′,4,4′-ODPA),4,4′-二氨基二苯醚(4,4′-ODA)和3,4’-二氨基二苯醚(3,4′-ODA)为原料合成了共聚酰亚胺,实验中还以邻苯二甲酸酐(PA)为分子量调节剂,制备了理论分子量为10000的共聚酰亚胺,主要研究了其热性能和结晶性能。结果表明,与均聚型聚酰亚胺(ODPA/4,4′-ODA为原料合成)比较,间位异构体3,4′-ODA的加入使聚酰亚胺的玻璃化转变温度降低。经过等温结晶处理后,能够在DSC测试中出现较明显的熔融峰,而且延长结晶时间或者升高结晶温度有利于晶体的进一步完善。但是当共聚单体3,4′-ODA的加入量增加到10%(摩尔比)时,即使经过较长时间的等温处理,该共聚酰亚胺依然为无定形结构。     

新型芳香聚脲准轮烷的合成与表征

以4,4′-二氨基二苯醚的-βCD包合物和甲苯-2,4-二异氰酸酯为单体,N,N-二甲基乙酰胺为溶剂,在室温合成了聚脲-βCD准轮烷(3a)。采用红外光谱(FT-IR)、热失重(TG)、核磁共振(1H-NMR)和X射线粉末衍射等手段分别对包合物和准轮烷(3a)进行了表征。结果表明,准轮烷(3a)链上-βCD的含量为42.9%(质量分数),热稳定性良好,是一类新颖的准轮烷。     

Substituent effect on color tuning of red light emission in photoluminescence and electroluminescence of red fluorophore

Typical small red light-emitting molecules for organic light emitting diodes (OLEDs) were highly susceptible to fluorescence concentration quenching in solid state. Red fluorophores, (2Z, 2'Z)-3, 3'-[4,4"-bis(dimethylamino)-1,1':4',1"-terphenyl-29',5'-diyl]bis(2-phenylacrylonitrile) (ABCV-P), (2E, 2'E)-3,3'-[4,4"-bis(dimethylamino)-1,1':4',1"-terphenyl-2',5'-diyl]bis[2-(2-thienyl)acrylonitrile] (ABCV-Th) and (2Z, 2'Z)-3,3'-[4,4"-bis(dimethylamino)-1,1':4',1"-terphenyl-2',5'-diyl]bis[2-(2-naphthyl)acrylonitrile] (ABCV-Np), capable of preventing fluorescence concentration quenching were designed and synthesized. These compounds have intramolecular charge transfer (ICT) properties which were estimated by measurement of UV-Visible absorption and photoluminescence (PL) emission spectra with variation of solvent polarity (n-Hexane/Chloroform = 99/1, 1/1; Chloroform; Methylene chloride). The magnitude of ICT for ABCV-Th was measured to be the largest and that for ABCV-Np was slightly larger compared to that for ABCV-P. The magnitude of ICT resulted in a shift of peak wavelength of PL emission. Therefore, this result well supported substituent effect on the color change of PL emission. The peak wavelengths of photoluminescence for ABCV-P, ABCV-Np and ABCV-Th were observed to be 607.5, 611.5 and 617.5 nm, respectively, and those of EL spectra were measured to be 612.5, 619.5, 621.0 nm, respectively. The emission maxima of PL and EL spectra for these red fluorescent compounds were well correlated with substituent effect on ICT for them.     

芳香族聚噻唑的结构与物理性能的研究

以二氨基二苯醚及二氨二苯甲烷为原料,通过一系列有机合成反应,制备出单体4,4′-二氨基-3,3′-二巯基二苯醚二氯化氢和4,4′-二氨基-3,3′-二巯基二苯甲烷二氯化氢。以多聚磷酸为溶剂,与对苯二甲酸、邻苯二甲酸和间苯二甲酸溶液聚合,合成四种不同的芳香族聚噻唑聚合物。通过对聚合物的耐热性能、结晶性能以及液晶行为的研究比较,发现四种聚合物都是耐热性较好的材料,但由于结构不同,它们的耐热性能、结晶性以及液晶行为有所不同。     

Thermal,optical, electrochemical,and electrochromic characteristics of novel polyimides bearing the Acridine Yellow moiety

A series of novel polyimides and copolyimides were obtained by combining 2,7-dimethylacridine-3,6-diamine with one of three aromatic dianhydrides: 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4′-(4,4′-isopropylidene-diphenoxy)bis(phthalic anhydride) and 4,4′-tetraphthaloyl-bis(1,8-naphthalene dicarboxylic)dianhydride. The resultant polymers showed glass transition temperatures (T_g) in the range 209–331 °C and decomposition temperature (T_d) in the range of 370–475 °C. The optical properties, absorption and photoluminescence (PL) of the obtained polymers were investigated in solution and in the solid state as blends with inert poly(methyl methacrylate). The polymers dissolved in NMP emitted blue or green light with the maximum emission wavelength in the range of 438–512 nm, while emitting blue light in the solid state. The electrochemical behavior of the polyimides was studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). They exhibited electrochemical band gap in the range of 1.36–2.94 eV.     

Photo/electroluminescence properties of an europium (III) complex doped in 4,4′-N,N′-dicarbazole-biphenyl matrix

The photoluminescence properties of one europium complex Eu(TFNB)₃Phen (TFNB = 4,4,4-trifluoro-1-(naphthyl)-1,3-butanedione, Phen = 1,10-phenanthroline) doped in a hole-transporting material CBP (4,4′-N,N′-dicarbazole-biphenyl) films were studied. A series of organic light-emitting devices (OLEDs) using Eu(TFNB)₃Phen as the emitter were fabricated with a multilayer structure of indium tin oxide, 250 Ω/square)/TPD (N,N′-diphenyl-N,N′-bis(3-methyllphenyl)-(1,1′-biphenyl)-4,4′-diamine, 50 nm)/Eu(TFNB)₃phen (x): CBP (4,4′-N,N′-dicarbazole-biphenyl, 45 nm)/BCP (2,9-dimethyl-4,7-diphenyl-l,10 phenanthroline, 20 nm)/AlQ (tris(8-hydroxy-quinoline) aluminium, 30 nm)/LiF (1 nm)/Al (100 nm), where x is the weight percentage of Eu(TFNB)₃phen doped in the CBP matrix (1-6%). A red emission at 612 nm with a half bandwidth of 3 nm, characteristic of Eu(III) ion, was observed with all devices. The device with a 3% dopant concentration shows the maximum luminance up to 1169 cd/m² (18 V) and the device with a 5% dopant concentration exhibits a current efficiency of 4.46 cd/A and power efficiency of 2.03 lm/W. The mechanism of the electroluminescence was also discussed.