结构型光敏聚酰亚胺的制备及研究

用均苯四甲酸二酐分别与1-(3-氨基苯基)-3-(4-氨基苯基)-2-丙烯-1-酮(光敏性二胺Ⅰ)和4,4’-二(2-间氨基苯甲酰基)乙烯基苯(光敏性二胺Ⅱ),经溶液聚合、化学亚胺化,制备了一类新型可溶性的结构型光敏聚酰亚胺。该合成方法简便,分子量容易控制,起始原料价廉易得,产品纯度与收率高。TGA,UV,GPC等研究结果表明,所制备的树脂曝光波长能与工Ⅰ业线匹配使用,具有良好的耐热性能与感光性能。     

结构型光敏二胺的合成与表征

利用微波反应合成了新型的光敏聚酰亚胺_的中间体光敏二胺(1,4-二[2-(4-氨基苯甲酰)乙烯基]苯),研究了光敏二胺的制备,并用核磁及元素、红外、紫外对其结构进行了表征,初步探讨了反应时间及反应温度的影响.     

9,10-Diphenylanthracene-containing poly(arylene ether sulfone)s with improved glass transition temperature and photocrosslinking properties

In this study, novel poly(arylene ether sulfone)s containing 9,10-diphenylanthracene units were synthesized and their thermal and optical properties were investigated. This new bisphenol monomer, 9,10-bis(4-hydroxyphenyl)anthracene, was facially synthesized in two steps and showed similar reactivity for SNAr reactions as other bisphenol monomers, such as bisphenol A. The introduction of an anthracene unit to poly(arylene ether sulfone)s can obviously improve glass transition temperature and retain good solubility and high decomposition temperatures. The glass transition temperature of poly(arylene ether sulfone) reached up to 265 °C when the bisphenol A was entirely substituted by bis(4-hydroxyphenol)anthracene. These polymers are soluble in chloroform, N,N-dimethylformamide and N-methyl-2-pyrrolodone and can be film-formed through spin-coating. Interestingly, anthracene units endowed these polymers with photocrosslinkable properties and further improved their thermal stability.     

酚酞型聚芳醚腈砜的合成与性能研究

以酚酞、２，６二卤苯甲腈、４，４’，二氯二苯砜和４，４’，二羟基二苯砜为主要原料进行共缩聚反应，合成了酚酞型聚芳醚腈砜（ＰＰ－ＰＥＮＳ）。采用红外光谱、热分析等方法对共聚物的结构、热氧稳定性和玻璃化转变温度进行了表征，并对酚酞结构单元含量和腈基含量对聚芳醚腈砜性能的影响进行了讨论     

Synthesis and characterization of a novel photocrosslinkable fluorinated poly(arylene ether) for optical waveguide

To improve its chemical resistance and mechanical stability, a novel fluorinated poly(arylene ether) bearing a photocrosslinkable chalcone group in the main chain was successfully synthesized by means of polycondensation between 4,4′-dihydroxychalcone and decafluorobiphenyl in N,N-dimethylacetamide in the presence of the excess anhydrous potassium carbonate. The structure of polymer was characterized by ¹H NMR and ¹⁹F NMR spectroscopies. The resulting polymer shows excellent solubility in common organic solvents, high glass transition temperature and good thermal stability. Crosslinking of the resulted polymer has been demonstrated by UV irradiation. Near-IR spectra of polymer film before and after UV irradiation show no absorption at the telecommunication wavelengths of 1310 and 1550 nm, demonstrating that the resulting polymer is good candidate material for optical waveguide application.     

磺化含侧苯基杂萘联苯聚醚砜质子交换膜材料的合成与性能

以4-(3-苯基-4-羟基苯基)-2,3-二氮杂萘-1-酮、4-(4-羟基苯基)-2,3-二氮杂萘-1-酮和4,4’-二氯二苯砜为单体,合成了一系列含侧苯基杂萘联苯聚醚砜,然后以浓硫酸为磺化剂,制备磺化含侧苯基杂萘联苯聚醚砜(SPPES-P)。采用FT-IR、1 H NMR对聚合物的结构进行了表征,表明磺酸基被成功地引入到聚合物侧链苯基上。采用溶液法制备了SPPES-P质子交换膜。考察了SPPES-P膜的吸水率、溶胀率、质子传导率,以及甲醇渗透性能和耐氧化性能,SPPES-P膜具有较好的阻醇性和耐氧化性能。     

Synthesis and characterization of novel photoactive poly(arylene ether ketone) with azobenzene pendants

A novel azobenzene-functionalized poly(arylene ether ketone) (azo-PAEK) with azo moieties on the pendants was prepared by post-esterification reaction of acid-containing poly(arylene ether ketone) (acid-PAEK) with 4-((4-nitrophenyl)diazenyl)phenol (NAP). DSC and TGA measurements indicate the azo-PAEK has high glass transition temperature of 152 °C and good thermal stability with 5% weight loss at 319 °C. Irradiated by 360 nm UV light, the azo-PAEK shows a significant photoisomerization effect. Under the illumination of linearly polarized laser beam, significant surface-relief-gratings (SRGs) with the surface modulation depth of 37 nm were fabricated rapidly on the azo-PAEK film.     

Synthesis and characterization of nitrated and aminated poly(phenylene sulfide) derivatives for advanced applications

Nitrated and aminated poly(phenylene sulfide) (PPS) derivatives with different extent of modification were synthesized in a one-pot reaction in suspension. Their substitution degree was determined from both elemental analysis and TGA curves. FT-IR and NMR spectra demonstrated the effectiveness of the functionalization reactions, showing the appearance of bands related to the substituent groups. A progressive reduction in thermal stability was observed as the number of functional groups increased. Aminated derivatives were thermally less stable and exhibited higher solubility in aprotic polar solvents than the corresponding nitrated polymers. DSC thermograms revealed a diminution in the crystallization temperature and a rise in the glass transition with increasing functionalization degree, since the presence of substituent groups inhibits the rotation of consecutive elements of the polymer chain. The level of crystallinity decreased upon increasing chain modification, as evidenced from X-ray diffractograms. The steric hindrance of the substituents disrupts the chain packing, leading to smaller crystals. These derivatives are expected to have applications in electromembranes and as matrix materials for the fabrication of high-performance composites suitable for structural and non-structural components.     

磺化聚醚砜上浆剂对碳纤维/聚醚砜复合材料界面性能的影响

为了提高碳纤维(CFs)增强热塑性树脂聚醚砜(PES)复合材料的界面结合力,对PES进行磺化改性,得到磺酸基聚醚砜(SPES)制备的CFs上浆剂,研究了SPES上浆剂对CFs/PES复合材料界面性能的影响和上浆剂质量分数对CFs/PES复合材料的作用效果。结果表明:经过SPES上浆的纤维毛丝量降低、耐磨性提高。同时FTIR和XPS分析表明:SPES中的—SO3H基团与CFs表面微量的活性官能团发生了化学反应,提高了增强体CFs与基体树脂PES间的黏连。当上浆剂含量为1wt%时,CFs/PES复合材料的层间剪切强度(ILSS)提高最显著,比未上浆改性的CFs/PES复合材料的提高了24%。SEM照片证实在此浓度下CFs与PES结合更加紧密。动态力学热分析(DMTA)结果亦证明1wt%的SPES上浆剂提高了CFs/PES复合材料的玻璃化转变温度。     

The intercalation of poly(methyl methacrylate)/aluminophosphate nanocomposites and the properties improvement

Poly(methyl methacrylate) (PMMA)/dodecylamine templated lamellar aluminophosphate (DDA-LAP) intercalated nanocomposites are prepared by in situ bulk polymerization of MMA. The intercalated structure is characterized. With the intercalation of DDA-LAP in PMMA matrix, the glass-transition temperatures of nanocomposites (T_g) are increased. The nanocomposites obtained keep relatively high transparency in optical property and have a significant improvement in mechanical properties and thermal stability. The mechanism for the properties enhancement is investigated. The strong interfacial interaction between the aluminophosphate layers and the PMMA chains, the homogeneously distribution and the graphitized char formation during heating are three key roles for the properties improvement.     

New fluorinated poly(ether sulfone imide)s with high thermal stability and low dielectric constant

A new aromatic diamine monomer with four pendant trifluoromethyl groups, 2,2′-bis{3-[3,5-di(trifluoromethyl)phenyl]-4-[4-amino-phenoxy]phenyl}sulfone (3), was successfully synthesized through free-radical substitution, Suzuki coupling and nucleophilic substitution reactions using bis(4-fluorophenyl)sulfone and N-bromosuccinimide as starting materials. Then it was employed to prepare a series of fluorinated poly(ether sulfone imide)s (PESIs 5a–c) with various commercial aromatic dianhydrides via a one-step high-temperature polycondensation. These polymers could be easily dissolved in some strong polar organic solvents, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide, chloroform, dichloromethane and tetrahydrofuran at room temperature. Flexible and transparent films can be obtained easily by solution casting. They had high thermal stability and didn't show significant weight loss up to temperature of approximately 530 °C in nitrogen and air atmospheres. They also revealed low dielectric constants with the values in the range of 2.74–2.90 at 1 MHz measured for their capacitance.     

含有叔胺结构的聚醚醚酮单体的合成

通过三步反应合成了一种具有叔胺结构的聚醚醚酮单体,其结构经1H NMR1、3CNMR、IR和元素分析确证,同时讨论了影响反应的因素。     

含二氮杂萘酮联苯结构新型聚芳酰胺的合成及性能研究

以一种甲氧基取代的新型含杂萘联苯结构的芳香二胺:2-(4-氨基苯基)-4-[3-甲氧基-4-(4-氨基苯氧基)苯基]-2,3-二氮杂萘-1-酮(OO-DA)为单体,采用Yamazaki体系,分别和3种芳香二酸进行溶液亲核缩聚反应,制得一类新型杂萘联苯型聚芳酰胺树脂,其特性粘度为0.89~1.03dL/g;以FT-IR1、H-NMR表征了聚合物的结构;利用DSC、TGA研究了聚合物的热性能,结果表明聚芳酰胺的玻璃化转变温度为281~307℃,氮气氛中5%热失重温度达440℃以上,800℃时残留质量>55%;在DMAC、NMP等极性非质子性溶剂中有良好的溶解性,所得聚酰胺膜的拉伸强度为69~93MPa,断裂伸长率8.65%~9.47%,拉伸模量1.49~1.78GPa,体积电阻率>1015Ω.cm。     

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.     

Preparation and thermal properties of soluble poly(phthalazinone ether sulfone ketone) composites reinforced with multi-walled carbon nanotube buckypaper

A nanocomposite with soluble high-performance poly(phthalazinone ether sulfone ketone) (PPESK) as matrix and multi-walled carbon nanotube buckypaper (MWCNT-BP) as reinforcement was fabricated by hot-press processing. The morphologies, dynamic and static mechanical behavior, thermal stability of the MWCNT-BP/PPESK composites were studied using scanning electron microscope (SEM), dynamic mechanical analyzer (DMA) and thermogravimetric analyzer (TGA). SEM microphotographs revealed a high impregnation degree of the MWCNT-BP/PPESK composites. Dynamic and static mechanical analysis revealed that the nanocomposites possessed high storage modulus, and good retention rate of mechanical strength even at 250 °C, which is mainly attributed to satisfied impregnation and strong interactions between MWCNT-BP and PPESK. Thermogravimetric analysis exhibited that the nanocomposites had excellent thermal stability. These investigations confirm that MWCNT-BP can be effectively used to manufacture high-loading CNT/PPESK composites with improved properties.     

主链含三苯胺链段的TPA-DHPPV共聚物的合成及表征

合成了2,5-二氯甲基-1,4-二己氧基苯、1,4-二己氧基-2,5-二甲苯双(三苯基氯化季膦)和4',4-三苯胺二醛3种单体.通过聚合反应制得了聚1,4-二己氧基对苯乙炔(DH-PPV)和含三苯胺链段的PPV类共聚物(TPA-DHPPV),对聚合物进行了结构表征和性能测试.DH-PPV和TPA-DHPPV聚合物物质结构准确,在紫外光激发下能发出强的蓝绿光,荧光光谱表征说明该类聚合物均能发射较强的荧光,电致发光器件的伏安特性测试表明该类聚合物具有较低的驱动电压和较高的发光亮度,并且该类聚合物具有较高的热稳定性.     

质子交换膜用部分含氟磺化聚芳醚的合成与性能研究

通过直接磺化的方法,合成了一种部分含氟的磺化聚芳醚.由于特殊单体结构的设计,在聚合物主链上引入甲基取代基,对聚合物主链进行保护.用氯磺酸直接磺化方法在聚芳醚侧基上引入磺酸功能基,实现了聚合物磺化结构的可控定位合成,得到了稳定性较好的磺化聚芳醚.用溶液浇膜法制备了质子交换膜,研究了膜的各种性能.这种膜具有较高的导电性、吸水性和好的抗水解性、热稳定性.由于特殊结构的设计和部分氟的引入,这种膜的抗氧化性有显著的提高.     

Synthesis,characterization and dielectric behavior of (ES)-form polyaniline/cerium(III)-nitrate-hexahydrate composites

In this study, morphological, thermal and dielectric properties of chemically synthesized polyaniline (PANI) and its cerium(III)-nitrate-hexahydrate (Ce(NO₃)₃·6H₂O) doped composites with various doping levels were investigated. Characteristic bands of emeraldine salt (ES)-form of PANI was clearly observed in UV–visible (UV–vis) and Fourier transform infrared (FTIR) spectroscopies. Thermal analyses carried out by Differential scanning calorimetry (DSC) indicated that there was a glass transition at about 70 °C and the doping process increased thermal stability of the polymer. In the surface morphologies examined by scanning electron microscopy (SEM), various microstructures depending on the doping level were observed. Real dielectric constant exhibited a significant decrease due to the increase in the doping level especially at higher frequencies. Conductivity mechanisms of PANI and its composites were investigated by universal power law as conventional models could not provide a complete picture for all the samples. Dramatic increases up to 45, 35 and 30 times in the conductivity of 10% doped PANI were observed for 300, 350 and 400 K, respectively.