聚芳醚腈砜的结构与热性能的研究

本文采用红外光谱方法对聚芳醚腈砜的结构进行了分析,并与间苯型聚芳醚砜的结构作了对比,利用ＴＧＡ,ＤＴＡ等热分析测试,对不同分子量聚芳醚腈砜的热氧稳定性,玻璃化转变温度等热性能进行了研究。     

聚芳醚腈砜碳布层压板和玻璃布层压板的研制

本文以２,６－二氟苯甲腈和４,４－二羟基二苯砜为主要原料合成了聚芳醚腈砜利用ＩＲ、＾１３Ｃ－ＮＭＲ和热分析等手段对其结构和热性能进行了表征。以取长醚腈砜为基体树脂采用特殊的溶液浸胶工艺,一次邓要制我含量达４５％的预浸料。制得的碳布层压板和玻璃布层压板皆具有优异的力学性能和热性能,可在１８０℃使用。     

氰基化钛酸钡对聚芳醚腈介电薄膜结构与性能的影响

首先通过化学接枝法在钛酸钡纳米粒子(BT)表面依次接枝了异佛尔酮二异氰酸酯(IPDI)和3-氨基苯氧基邻苯二甲腈(3-APN),得到氰基功能化的钛酸钡纳米粒子(BT-CN);接下来,将其与聚芳醚腈(PEN)复合,制备了聚芳醚腈/氰基化钛酸钡复合介电薄膜。通过傅里叶红外光谱(FTIR)、X射线光电子能谱(XPS)、热重分析仪(TG)证实了BT成功进行了表面功能化。此外,BT-CN的加入可以有效增强PEN复合薄膜的热学、力学和介电性能;相较于纯PEN,复合薄膜的玻璃化转变温度增加了12℃,拉伸强度提高了9.6%,1 kHz时介电常数提高了227.8%。综上所述,氰基功能化有利于改善有机-无机界面相容性,从而进一步提高复合薄膜的综合性能。     

聚芳醚腈/TiO2杂化薄膜的制备及其介电性能

通过溶胶一凝胶法原位合成具有较高介电常数的聚芳醚腈的TiO2杂化薄膜,采用红外光谱、X射线光电子能谱和扫描电子显微镜分析表明,TiO2以纳米粒径均匀分散在薄膜中。薄膜的介电常数与TiO2的含量呈线性增长关系,在ω(TiO2)为20％时达到6．21,并且介电强度没有明显的下降。综合各项性能分析显示ω(TiO2)为15％的杂化薄膜具有优良的力学性能、热性能和介电性能。     

氰基含量对聚芳醚腈砜性能的影响

以2,6-二氟苯甲腈、4,4’-二氯二苯砜、4,4’-二羟基二苯砜以及间苯二酚为主要原料,改变它们的摩尔配比合成了不同氰基含量的聚芳醚腈砜。研究了氰基含量对聚芳醚腈砜的合成工艺、聚集态结构、热氧稳定性以及玻璃化转变温度的影响。     

耐高温含氟聚芳醚酮和聚芳醚砜的合成与性能研究

通过三步反应合成新的含氟双酚单体3,4-二氟苯基对苯二酚,由该含氟双酚单体、4-氟苯基对苯二酚、邻苯基对苯二酚分别与4,4′-二氟二苯酮、4,4′-二氯二苯砜经亲核缩聚反应,制备了一系列新型聚芳醚酮和聚芳醚砜。采用 FT-IR、DSC、TGA及XRD手段等对聚合物的结构和性能进行了表征和研究,结果表明：合成的聚芳醚酮和聚芳醚砜具有优异的耐热性能,玻璃化转变温度分别在150~159 ℃和177~196 ℃之间,氮气中5 %热失重温度分别在527 ℃和507 ℃以上。合成的聚芳醚酮和聚芳醚砜具有良好的溶解性,室温下能溶解在N-甲基吡咯烷酮、二甲基乙酰胺、氯仿等有机溶剂中。     

聚芳醚腈/富勒烯复合薄膜制备与性能研究

以聚芳醚腈树脂为基体、富勒烯为纳米功能填料制备了聚芳醚腈介电功能复合薄膜。首先通过共溶剂控制蒸发法制备了聚芳醚腈/富勒烯低介电薄膜。着重分析了共溶剂控制蒸发分散方法对富勒烯分散效果以及薄膜性能的影响。研究发现:利用聚合物大分子链与填料粒子逐渐相互缠结的原理,共溶剂控制蒸发法对于制备可溶解性纳米填料的复合材料可以达到极佳的分散效果,获得的复合薄膜不仅具有低于2.0的介电常数,而且其热性能和力学性能都得以提高。     

特种工程塑料—聚芳醚腈

本文介绍了特种工程塑料聚芳醚腈的合成，性能，成型及应用方面的研究，并讨论了合成的应及结构与性能的关系。     

聚芳醚砜酮纤维的热性能

采用DSC、TG测定了含联苯结构聚芳醚砜酮 (PPESK)纤维的热性能 ,结果表明 ,纤维的玻璃化温度随砜酮比的增大而提高 ,纤维的起始分解温度大于 463℃。当砜酮比为 15 / 85 ,5 0 / 5 0 ,75 / 2 5时 ,纤维的玻璃化温度分别为 2 5 7.62 ,2 78.64 ,2 79.71℃ ;热分解活化能分别为 15 0 .8,2 19.9,195 .5kJ/mol;热分解反应级数分别为 1,1.76,1级     

酚酞型聚芳醚腈的合成与性能

以二氟苯甲腈、酚酞及对苯二酚为原料，制备了无定形酚酞型聚芳醚腈树脂，其玻璃化转变温度在２００℃以上。采用流涎法制备了酚酞型聚芳醚腈薄膜。对薄膜样品进行了红外光谱分析和热分析，测定了力学性能，在扫描电子显微镜上观察了薄膜拉伸断面。结果表明：（１）合成产物具有聚芳醚腈结构；（２）由于腈侧基的引入，酚酞型聚芳醚腈及其共聚物的热性能和力学性能均有提高并且随共聚物中对苯二酚用量的增加而增加；（３）ＳＥＭ形貌表明三种样品的断裂形态结构存在着很大差别，当酚酞／对苯二酚＝１１时断面有取向伸长特征，致使应力传递沿分子链伸长方向扩展，表现出较大的拉伸强度和断裂韧性。     

Poly(arylene ether nitrile) copolymers containing pendant phenyl: Synthesis and properties

A series of poly(arylene ether nitrile) copolymers (PENAPs) were synthesized with bisphenol A (BP-A), bisphenol AP (BP-AP) and 2,6-Dichlorobenzonitrile (DCBN) via a nucleophilic substitution polycondensation reaction. FTIR and ¹H-NMR were used to confirm the structure of PENAPs. Glass transition temperature (T_g) of PENAPs determined by differential scanning calorimetry (DSC) ranged from 154.2 to 200.8°C. The 5% weight lost temperature (T_5%) of PENAPs were 418.9–447.7°C. The tensile and DMA test indicated that PENAPs possessed excellent mechanical properties with tensile strength more than 92.8 MPa and storage modulus more than 1.0 GPa at about 150°C. The melt flowability was measured by rheology properties testing ranging from 80 to 1639 GPa at 290°C and under shear frequency 100 Hz, which indicated the copolymers had good flowability and thermal stability. Additionally, PENAPs could be dissolved in many solutions, which meant PENAPs had good solubility and can be processed by solution method.     

Poly(arylene ether sulfone) multi-block copolymers bearing perfluoroalkylsulfonic acid groups

Poly(arylene ether sulfone) (PAES) multi-block copolymers bearing perfluoroalkylsulfonic acid moieties were prepared from hydrophilic and hydrophobic prepolymers. The latter were synthesized by reaction of N,N-diisopropylethylammonium 2,2-bis(p-hydroxyphenyl)pentafluoropropanesulfonate (HPPS) with bis-(4-fluorophenyl) sulfone (FPS), and biphenol (BP) with FPS, respectively. Prepolymers and multi-block copolymers were prepared at 180 °C in N,N-dimethylacetamide in the presence of K₂CO₃. The prepolymers were reacted overnight; the multi-block copolymers were reacted only 80 min to minimize transetherification. Prepolymers and multi-block copolymers were characterized using ¹H and ¹³C NMR. ¹⁹F NMR provided molecular weight of hydrophilic prepolymers bearing aryl fluoride end groups. GPC was used to characterize the multi-block copolymers. Copolymer block lengths were determined by quantifying ¹³C NMR peak areas of quaternary carbon atoms adjacent to sulfur in FPS moieties. Hydrophilic and hydrophobic block lengths were in the range 9.4-23.4 and 4.4-11.8 repeating units, respectively. AFM showed phase separation for all block lengths. Conductivity at 80 °C and 100% relative humidity ranged from 6.2 to 34.3 mS/cm, with the best value obtained for hydrophilic/hydrophobic block lengths of 13.3/6.0.     

Multiblock poly(arylene ether nitrile) disulfonated poly(arylene ether sulfone) copolymers for proton exchange membranes: Part 1 synthesis and characterization

A series of multiblock copolymers based upon alternating segments of a hydrophilic disulfonated poly(arylene ether sulfone) and a hydrophobic fluorine-terminated poly(arylene ether benzonitrile) (6FPAEB) were synthesized and characterized for use as proton exchange membranes (PEM). The ion-exchange capacity of the block copolymers were varied by utilizing 4,4′-biphenol or hydroquinone in combination with 3,3′-disulfonated-4,4′-dichlorodiphenyl sulfone (SDCDPS) to form the hydrophilic segments. The alternating block copolymer morphology was achieved by using mild temperatures to link the oligomers together and minimize ether–ether interchange reactions. Both the 4,4′-biphenol and hydroquinone based membranes showed high proton conductivity with moderate water uptake and good mechanical properties. The block copolymers displayed nanophase separated morphologies, confirmed by transmission electron microscopy (TEM) and small angle x-ray scattering (SAXS). The strong membrane performance was attributed to the multi-phase morphology.     

Partially Fluorinated Multiblock Poly(arylene ether sulfone) Membranes for Fuel Cell Applications

Sulfonated poly(arylene ether sulfone) (SPAES‐F series) membranes, which are partially fluorinated multiblock polymers containing Bisphenol 6F (6F‐BPA), are synthesized. The membranes exhibit less water uptake and higher ion conductivity at similar ion exchange capacity (IEC) values compared to previous SPAES membranes containing identical hydrophilic blocks. This is attributed to the presence of 6F‐BPA in the hydrophobic block, which enhances hydrophobicity and promotes phase separation, as observed through transmission electron microscopy analysis. F4 (IEC = 2.4 meq g^?1) shows superior ion conductivity than Nafion NRE212 membrane irrespective of the humidity level. Furthermore, the SPAES electrolyte membrane of 1.5 meq g^?1 produces better performance than NRE212, yielding a current density of 488 mA cm^?2 at 80 °C, 80% RH, and 0.6 V. In 50% RH at 80 °C, SPAES with 1.5 meq g^?1 exhibits a cell resistance and fuel cell performance comparable to those of NRE212; clearly, regulating hydrophobicity and hydrophilicity is crucial for enhanced performance.     

含Cardo基三元共聚芳醚砜的合成

以酚酞,双酚A,4,4’-二氯二苯砜为原料,采用碱性条件下亲核取代、逐步缩聚的方法合成了一系列新型的主链上含Cardo基的三元共聚芳醚砜。采用傅里叶变换红外光谱仪、核磁共振氢谱仪、差示扫描量热仪、热重分析仪、凝胶渗透色谱仪等表征了含Cardo基三元共聚芳醚砜的结构并研究了其热性能。结果表明:含Cardo基三元共聚芳醚砜为非晶态,其玻璃化转变温度为171~258℃,在氮气中质量损失5%时的温度均高于395℃;在强极性非质子溶剂及普通有机溶剂中均具有较好的溶解性;相对分子质量为(1.0~2.1)×104,相对分子质量分布为2.23~3.49。     

Synthesis,Characterization and Properties of New Semifluorinated Poly(arylene ether phosphine oxide)s

Bis(4‐fluoro‐3‐trifluoromethylphenyl)phenylphosphine oxide is synthesized and six new poly(arylene ether)s are prepared by nucleophilic displacement of the fluorine atom on the benzene ring by several diphenols under basic conditions. The products show very high glass transition temperatures of up to 252 °C and very good thermal stabilities of up to 490 °C for 5% weight loss. The polymers display very low heat release rates in the microscale combustion calorimeter test, suggesting good flame retardance. All polymers are soluble in a wide range of organic solvents. Transparent thin films cast from dichloromethane exhibit tensile strengths up to 54 MPa, a modulus of elasticity up to 0.97 GPa and elongation at break up to 47% depending on their exact repeating unit structures.

     

Poly(arylene ether sulfones) and poly(arylene ether ketones) derived from dibenzofuran

Summary New polyarylene ether ketones and polyarylene ether sulfones were prepared by polycondensation of various bisphenols with two new dihalide monomers including dibenzofuran structure, respectively 3,6 bis (4-fluorophenylcarbonyl) dibenzofuran and 3,6 bis (4-fluorophenylsulfonyl) dibenzofuran. Most of these thermoplastic polyethers are soluble in NMP and in chlorinated soluents. They exhibit Tgs up to 234°C for the polyetherketones and up to 262°C for the polysulfones, so over 50°C higher than the Tgs of classical available polyethers.     

成盐剂体系对聚醚砜树脂合成与性能的影响

通过缩聚系统研究了成盐剂体系中的K2CO3:Na2CO3配比及成盐剂过量比和平均粒径等参数对聚醚砜(PESU)树脂合成过程中成盐反应时间、溶液黏度的影响,并利用高压毛细管流变仪和高温注塑方法对合成的PESU热稳定性和颜色等级进行了测试和对比研究.研究发现,成盐剂最优配方为复合成盐剂体系K2CO3:Na2CO3物质的量之...     

Synthesis and characterization of polyurethanes containing arylene sulfone ether linkages

Polyurethanes containing arylene sulfone ether linkages were synthesized by solution polymerization of 4,4′-bis(4-isocyanatophenoxy)diphenylsulfone (SPI) and 4,4′-bis(3-isocyanatophenoxy)diphenylsulfone (SMI) with various aliphatic glycols such as ethylene glycol (EG), 1,2-propylene glycol (PG), 1,4-butylene glycol (BG), polyethylene glycol (PEG 300 and 1000), polypropylene glycol (PPG 300 and 1000) and polytetramethylene glycol (PTMG 1000. TERACOL) in dimethylacetamide (DMAC) at 120°C. The diisocyanates SPI and SMI were prepared from the corresponding diacid chlorides via Curtius rearrangement. The polyurethanes were obtained in high yields. The effect of structures of diisocyanate and aliphatic diols on the molecular weight and thermal properties of polyurethanes was also investigated. The polyurethanes prepared were characterized by infrared spectroscopy, solution viscosity, elemental analysis, thermogravimetric analysis and X-ray diffraction. Physical and thermal properties of polyurethanes prepared from SPI and various aliphatic glycols were compared with the polyurethanes from SMI and various aliphatic glycols.     

新型聚芳醚砜共聚物的制备及其性能

以4,4’-二氯二苯砜、4,4’-二羟基二苯砜和2,4-二羟基二苯砜为单体,通过缩聚合成一系列主链含异构体醚键单元的聚芳醚砜共聚物,利用核磁共振碳谱(13C NMR)、差示扫描量热分析(DSC)和高压毛细管流变仪对产物进行了测试和分析。对比不同产物的熔体黏度、玻璃化转变温度和力学性能,发现随着共聚单元含量的增加,聚芳醚砜共聚物的流动性逐渐提高,玻璃化转变温度逐渐降低,并且屈服点伸长率和缺口冲击强度均逐渐提高。这一结果对实际应用中提高聚芳醚砜树脂流动性和韧性、降低热加工温度等具有重要的指导意义。